Process for producing polyolefin resin composition and polypropylene composition

ABSTRACT

A process for producing a polyolefin-based resin composition comprises, in the first polymerization stage, polymerizing an α-olefin having 4 to 20 carbon atoms, a styrene or a cyclic olefin in the presence of a specific catalyst and, in the second polymerization stage, copolymerizing the obtained polymer with an α-olefin having 2 to 20 carbon atoms, a styrene or a cyclic olefin in the presence of a polyene. A polypropylene composition has a branching parameter a and a branching index g in specific ranges. The curve showing the change in viscosity under elongation with time, the degradation parameter D or the content of a high molecular weight component is specified. The polyolefin-based resin composition exhibits excellent uniformity and improved workability in melting due to improved tension in melted condition. The polypropylene composition exhibits excellent melting elasticity and secondary workability and provides foamed molded articles, sheets and blow molded articles.

TECHNICAL FIELD

The present invention relates to a process for producing apolyolefin-based resin composition, a polypropylene composition andapplications thereof. More particularly, the present invention relatesto a process for producing a polyolefin-based resin composition whichexhibits an improved workability in molding, which is advantageouslyused in the fields where excellent workability is required such as thesheet molding, the extrusion expansion molding, the blow molding, theprofile extrusion molding and the inflation molding and which cancontrol physical properties in a wide range. The present invention alsorelates to a polypropylene composition which exhibits excellent meltingelasticity, suppressed degradation of the resin in recycling to enablereusing and an excellent property for extrusion, emits no smell, causingno effects on the taste of foods, has excellent secondary workability,contains no gel, and provides inexpensive polypropylene sheets, blowmolded articles and foamed molded articles of polypropylene; andapplications of the polypropylene composition.

BACKGROUND ART

Taking advantage of the excellent weatherability due to chemicalstability, the excellent chemical resistance and the excellentmechanical strength, polyolefin resins have been provided with desiredphysical properties and desired shapes in accordance with variousmolding processes such as the sheet molding, the film molding, theinjection molding, the blow molding, the expansion molding, the vacuummolding and the rotation molding and have been widely used in variousfields.

Recently, the decrease in the load on the environment is continuouslyrequired for every type of plastics due to the enhanced consciousnessfor protection of the environment. Since polyolefin-based resins haveexcellent properties for recycling, can be molded easily and do not emitharmful components during incineration, the polyolefin-based resins areattracting the attention as the most suitable material for decreasingthe load on the environment. Therefore, it is estimated that thepolyolefin-based resins are used more widely and required to have highlyexcellent properties.

To satisfy the above requirement, it is necessary that the workabilityin molding of the polyolefin resins is further improved and moreexcellent mechanical properties be exhibited. As a means to achievethese improvements, formation of composites has been attempted but isinsufficient for improving the molding ability and exhibiting novelphysical properties.

As the means for improving the molding ability, a process for producinga polyolefin-based resin using a polyene component is known. However,since the polyolefin-based resin is produced in accordance with a singlestage polymerization process, the structure of the polymer is controlledessentially by adjusting the relative amounts of the monomer and thepolyene used for the polymerization and there are no other effectivemeans for the control. An increase in the amount of the polyene toimprove the melting property is accompanied with frequent gelation andformation of insoluble products and, as the result; the improvement inthe melting property is not achieved as desired. Moreover, a drawbackarises in that, in accordance with the single stage polymerizationprocess, the polyene cannot be copolymerized as desired in the effectiverange of the molecular weight distribution since the polyene is presentin all ranges of the molecular weight distribution. For example,although it is necessary that the polyene be present in a small amountin the range of the high molecular weight to improve the meltingproperty to a great degree, the amount of the polyene cannot becontrolled in the desired manner. Therefore, the polyene must be used inan amount more than necessary to improve the melting property andfrequent gelation and formation of insoluble products take place.

To overcome the above problem, multi-stage polymerization processes areproposed. In Japanese Patent Application Laid-Open Nos. Heisei8(1996)-92337, Heisei 8(1996)-100036, Heisei 8(1996)-311136 and Heisei9(1996)-235337, processes using polyenes for improving the balancebetween rigidity and impact strength of block copolymers containingpropylene as the main component are disclosed. In these processes,propylene-based block copolymers are obtained by copolymerizingpropylene and ethylene continuously after the homopolymerization ofpropylene. As the physical property of the resultant copolymer, thebalance between rigidity and impact strength is improved. However,nothing is mentioned on the form of the reaction and the specificprocedures of the process in the second stage that are important for theimprovement in the property for melt molding. In the above processes,although the molecular weight of the block copolymer itself ismentioned, none of the control of the molecular weight, the selection ofthe catalyst in each stage and the type of the monomer in the secondstage, which are the important factors for the improvement in themolding ability, are mentioned, either.

In WO 94/19382, a process for producing a propylene-based blockcopolymer using a diene is disclosed. As the characteristics of theprocess, an improvement in the balance between rigidity and impactresistance, an increase in the activation energy of melt flow, adecrease in the amount of gel components and the formation of anunsaturated group suitable for the macromolecular reaction aredescribed.

However, the above process is limited to the production of apropylene-based block copolymer. Although the improvement in the meltingproperty and the decrease in the amount of gel components are described,nothing is mentioned on the control of the multi-stage polymerizationand, therefore, no remarkable improvement in the melting property can beexpected. Nothing is mentioned on the uniform polymer composition in theabove process.

Polypropylene has been widely used in various fields taking advantage ofthe excellent properties such as high rigidity, excellent heatresistance, lightweight, low price and excellent properties for theenvironment. However, it has been difficult due to the small tension inmelted condition that applications are developed in the field ofextrusion molding such as the sheet molding, the blow molding and theexpansion molding. To improve the tension in melted condition, a processfor obtaining a branched polypropylene by irradiation with electronbeams is proposed (Japanese Examined Patent Publication No. 2655915).However, this process has drawbacks in that the facility is expensiveand the production cost increases and that the resin is degraded(scission of molecular chains) in an extruder and the reuse ofpolypropylene becomes difficult.

As the process for producing polypropylene having a high meltingelasticity, processes such as (i) a multi-stage polymerization (JapanesePatent Application Laid-Open No. Showa 58(1983)-219207), (ii)copolymerization with a polyene (Japanese Patent Application Laid-OpenNo. Heisei 8(1996)-92317), (iii) addition of an organic peroxide(Japanese Patent Application Laid-Open No. Heisei 7(1995)-138422), and(iv) irradiation with electron beams (Japanese Patent ApplicationLaid-Open No. Showa 62(1987)-121704) are proposed. However, the processdescribed in the foregoing item (i) has a drawback in that gel is formeddue to tension in melted condition. The process described in theforegoing item (ii) has a drawback in that gel is formed and thesecondary workability such as heat molding is adversely affected. Theprocess described in the foregoing item (iii) has a drawback in that thehandling property is poor and coloring and smelling take place. Theprocess described in the foregoing item (iv) has a drawback in that thefacility is expensive and the resin is degraded during recycling.

DISCLOSURE OF THE INVENTION

Under the above circumstances, the present invention has a first objectof providing a process for producing a polyolefin-based resincomposition which exhibits an improved workability in molding ofpolyolefins, is advantageously used in the fields where excellentworkability is required such as the sheet molding, the extrusionexpansion molding, the blow molding, the profile extrusion molding andthe inflation molding and can control physical properties in a widerange.

The present invention has a second object of providing a polypropylenecomposition which exhibits excellent melting elasticity, suppresseddegradation of the resin in recycling to enable reusing and an excellentproperty for extrusion, emits no smell, causing no effects on the tasteof foods, has excellent secondary workability, contains no gel andprovides inexpensive polypropylene sheets, blow molded articles andfoamed molded articles of polypropylene.

The present invention has a third object of providing applications forthe above polypropylene composition.

As the result of extensive studies by the present inventors to achievethe above objects, it was found that the first object could be achievedby producing a specific polyolefin-based resin composition in thepresence of a polyene in a specific amount in the second polymerizationstage in the two-stage polymerization process in the presence of aspecific catalyst or in the presence of a polyene in the secondpolymerization stage in the two-stage polymerization in the presence ofa specific catalyst, that the second object could be achieved by using apolypropylene composition satisfying specific parameters, and that thethird object could be achieved by conducting the blow molding, theexpansion molding or the sheet molding using the above polypropylenecomposition.

The present invention has been completed based on the above knowledge.

The present invention provides:

-   (1) A process for producing a polyolefin-based resin composition    which comprises:

in a first polymerization stage, polymerizing or copolymerizing at leastone monomer selected from ethylene, propylene, α-olefins having 4 to 20carbon atoms, styrenes and cyclic olefins in a presence of a catalystcomprising a combination of a catalyst component (A) comprising at leastone compound selected from compounds of transition metals of Group 4 ofthe Periodic Table having a cyclopentadienyl skeleton structure and apromoter component (B); and

in a second polymerization stage, copolymerizing the homopolymer or thecopolymer obtained in the first polymerization stage with at least onemonomer selected from ethylene, propylene, α-olefins having 4 to 20carbon atoms, styrene and cyclic olefins in a presence of a polyenehaving at least two polymerizable carbon-carbon double bonds in onemolecule in an amount of 1.0×10⁻⁷ to 1.0×10⁻³ moles per 1 g of thepolymer or the copolymer obtained in the first polymerization stage(hereinafter, this process will be referred to as process I);

-   (2) A process for producing a polyolefin-based resin composition    which comprises:

in a first polymerization stage, polymerizing or copolymerizing at leastone monomer selected from ethylene, propylene, α-olefins having 4 to 20carbon atoms, styrene and cyclic olefins in a presence of a catalystcomprising a catalyst component (A) comprising at least one compoundselected from compounds of transition metals of Group 4 of the PeriodicTable having a cyclopentadienyl skeleton structure and a promotercomponent (B); and

in a second polymerization stage, copolymerizing the homopolymer or thecopolymer obtained in the first polymerization stage with at least onemonomer selected from ethylene, α-olefins having 4 to 20 carbon atoms,styrene and cyclic olefins in a presence of a polyene having at leasttwo polymerizable carbon-carbon double bonds in one molecule(hereinafter, this process will be referred to as process II);

-   (3) A process for producing a polyolefin-based resin composition    comprising:

in a first polymerization stage, polymerizing or copolymerizing at leastone monomer selected from ethylene, propylene and α-olefins having 4 to20 carbon atoms in a presence of a catalyst comprising a combination ofa catalyst component (X) comprising a titanium trichloride-basedcompound or a component comprising titanium, magnesium and a halogen asessential components and an organoaluminum compound (Y), and

in a second polymerization stage, copolymerizing the homopolymer or thecopolymer obtained in the first polymerization stage with at least onemonomer selected from ethylene, propylene and α-olefins having 4 to 20carbon atoms in a presence of a polyene having at least twopolymerizable carbon-carbon double bonds in one molecule; and

the produced composition satisfying following requirements (a) to (c):

-   -   (a) a ratio [η]₂/[η]₁=1.05 to 10, wherein [η]₁ represents an        intrinsic viscosity of a polyolefin obtained in the first        polymerization stage and [η]₂ represents an intrinsic viscosity        of a polyolefin obtained in the second polymerization stage,    -   (b) a content of the polyolefin obtained in the second        polymerization stage in the polyolefin-based resin composition        is 0.001 to 80% by weight, and    -   (c) no insoluble components are present in a dissolution test of        the polyolefin-based resin composition using decaline at 135° C.        as a solvent (hereinafter, this process will be referred to as        process III);

-   (4) A polypropylene composition which satisfies following    requirements (i) to (iv):

(i) a branching parameter a is in a range of:

-   -   0.35<a≦0.57

(ii) an branching index g is in a range of:

-   -   0.75≦g<1.0 (when a molecular weight measured in accordance with        a light scattering method is 2,000,000 to 10,000,000)    -   090≦g<1.0 (when a molecular weight measured in accordance with a        light scattering method is 500,000 to a value smaller than        2,000,000)

(iii) an upturn from an inflection point is present in a curve showing achange in viscosity under extension with passage of time, and

(iv) a degradation parameter D is:

-   -   D≧0.7        (hereinafter, this composition will be referred to as        polypropylene composition I);

-   (5) A polypropylene composition which satisfies following    requirements (i) to (iii):

(i) a branching parameter a is in a range of:

-   -   0.35<a≦0.57

(ii) an branching index g is in a range of:

-   -   0.75≦g<1.0 (when a molecular weight measured in accordance with        a light scattering method is 2,000,000 to 10,000,000)    -   090≦g<1.0 (when a molecular weight measured in accordance with a        light scattering method is 500,000 to a value smaller than        2,000,000)

(iii) a content of a high molecular weight component having a molecularweight of 1,000,000 or greater as measured in accordance with a lightscattering method is 10% by weight or smaller

(hereinafter, this composition will be referred to as polypropylenecomposition II);

-   (6) A molded article which is obtained by using polypropylene    composition I or II: and-   (7) A thermoplastic resin composition which is obtained by adding a    thermoplastic resin to at least one composition selected from    polyolefin-based resin compositions obtained in accordance with any    one of processes I, II and III and polypropylene compositions I and    II.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a diagram exhibiting the change in the viscosity underextension of a polypropylene composition with passage of time.

THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION

The process for producing a polyolefin-based resin composition of thepresent invention includes two embodiments that are a process referredto as process I or process II and process III. The process referred toas process I or process II will be described first.

In the process for producing a polyolefin-based resin composition of thepresent invention, catalyst component (A) in the catalyst used inprocess I and process II comprises at least one compound selected fromcompounds of transition metals of Group 4 of the Periodic Table having acyclopentadienyl skeleton structure. Examples of the compounds oftransition metals of Group 4 of the Periodic Table having acyclopentadienyl skeleton structure include Components (A-1) to (A-5)shown in the following.

Components (A-1), (A-2) and (A-3):

Components (A-1), (A-2) and (A-3) are transition metal compoundsrepresented by the following general formulae (I), (II) and (III),respectively:CpM¹R¹ _(a)R² _(b)R³ _(c)   (I)CP₂M¹R¹ _(a)R² _(e)   (II)(Cp-A-Cp)M¹R¹ _(d)R² _(e)   (III)In general formulae (I), (II) and (III), M¹ represents a transitionmetal of Group 4 of the Periodic Table, Cp represents a group selectedfrom cyclopentadienyl group, substituted cyclopentadienyl groups,indenyl group, substituted indenyl groups, tetrahydroindenyl group,substituted tetrahydroindenyl groups, fluorenyl group and substitutedfluorenyl groups, R¹, R² and R³ each independently represent a ligand, Arepresents a crosslinking with a covalent bond, a, b and c eachrepresent an integer of 0 to 3, d and e each represent an integer of 0to 2, two or more ligands represented by R¹, R² and R³ may be bondedwith each other and form a ring, and two Cp in general formula (II) and(III) may represent a same group or different groups.

Examples of the transition metal of Group 4 of the Periodic Tablerepresented by M¹ in general formulae (I), (II) and (III) includetitanium, zirconium and hafnium.

Examples of the substituent on the ring of the group represented by Cpinclude hydrogen atom, halogen atoms, hydrocarbon groups having 1 to 20carbon atoms and hydrocarbon atoms having 1 to 20 carbon atoms andhalogen atoms. Substituents adjacent to each other may be bonded to eachother and form a ring. Examples of the halogen atom include fluorineatom, chlorine atom, bromine atom and iodine atom. Examples of thehydrocarbon group having 1 to 20 carbon atoms include alkyl groups suchas methyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, isobutyl group, tert-butyl group, n-hexyl group and n-decylgroup; aryl groups such as phenyl group, 1-naphthyl group and 2-naphthylgroup; and aralkyl groups such as benzyl group. Examples of thehydrocarbon group having 1 to 20 carbon atoms and halogen atoms includegroups obtained by substituting at least one hydrogen atom in the abovehydrocarbon group with a suitable halogen atom.

Examples of the substituted cyclopentadienyl group includemethylcyclopentadienyl group, ethylcyclopentadienyl group,isopropyl-cyclopentadienyl group, 1,2-dimethylcyclopentadienyl group,tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group,1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienylgroup, pentamethylcyclopentadienyl group andtrimethylsilyl-cyclopentadienyl group. Examples of the group having aring formed by substituents adjacent to each other include4,5-benzoindenyl group, α-acetoindenyl group and these compoundssubstituted with alkyl groups having 1 to 10 carbon atoms when the groupis based on the indenyl ring.

In the above formulae (I) to (III), R¹, R² and R³ each independentlyrepresent a ligand such as a ligand forming a σ-bond, a ligand forming achelate and a Lewis base. Examples of the ligand forming a σ-bondinclude hydrogen atom, oxygen atom, halogen atoms, alkyl groups having 1to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, arylgroups, alkylaryl groups and arylalkyl groups each having 6 to 20 carbonatoms, acyloxyl groups having 1 to 20 carbon atoms, allyl group,substituted allyl groups and substituents having silicon atom. Examplesof the ligand forming a chelate include acetylacetonato group andsubstituted acetylacetonato groups. A plurality of the ligandsrepresented by R¹, R² and R³ may be bonded to each other and form a ringwhen the plurality of the ligands are present. When the grouprepresented by Cp has a substituent, it is preferable that thesubstituent is an alkyl group having 1 to 20 carbon atoms.

Examples of the ligand represented by R¹, R² and R³ include halogenatoms such as fluorine atom, chlorine atom, bromine atom and iodineatom; alkyl groups having 1 to 20 carbon atoms such as methyl group,ethyl group, n-propyl group, isopropyl group, n-butyl group, octyl groupand 2-ethylhexyl group; alkoxyl groups having 1 to 20 carbon atoms suchas methoxyl group, ethoxyl group, propoxyl group, butoxyl group andphenoxyl group; aryl groups, alkylaryl groups and arylalkyl groupshaving 1 to 20 carbon atoms such as phenyl group, tolyl group, xylylgroup and benzyl group; acyloxyl groups having 1 to 20 carbon atoms suchas heptadecylcarbonyloxyl group; substituents having silicon atom suchas trimethylsilyl group and (trimethylsilyl)methyl group; and Lewisbases, examples of which include ethers such as dimethyl ether, diethylether and tetrahydrofuran; thioethers such as tetrahydrothiophene;esters such as ethyl benzoate; nitriles such as acetonitrile andbenzonitrile; amines such as trimethylamine, triethylamine,tributylamine, N,N-dimethyl-aniline, pyridine, 2,2′-bipyridine andphenanthroline; phosphines such as triethylphosphine andtriphenylphosphine; chain unsaturated hydrocarbons such as ethylene,butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives ofthese compounds; and cyclic unsaturated hydrocarbons such as benzene,toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene,cyclooctatetraene and derivatives of these compounds.

Examples of the crosslinking with a covalent bond represented by A ingeneral formula (III) include crosslinking with methylene group,crosslinking with dimethylmethylene group, crosslinking with ethylenegroup, crosslinking with 1,1′-cyclohexylene group, crosslinking withdimethylsilylene group, crosslinking with dimethylgermylene group andcrosslinking with dimethylstannylene group.

Component (A-1)

Examples of the compound represented by general formula (I) [component(A-1)] include (1) (pentamethylcyclopentadienyl)-trimethylzirconium, (2)(pentamethylcyclopentadienyl)triphenylzirconium, (3)(pentamethylcyclopentadienyl)tribenzylzirconium, (4)(pentamethylcyclopentadienyl)trichlorozirconium, (5)(pentamethylcyclopentadienyl)trimethoxyzirconium, (6)(cyclopentadienyl)trimethylzirconium, (7)(cyclopentadienyl)triphenylzirconium, (8)(cyclopentadienyl)tribenzylzirconium, (9)(cyclopentadienyl)trichlorozirconium, (10)(cyclopentadienyl)trimethoxyzirconium, (11)(cyclopentadienyl)dimethyl(methoxy)zirconium, (12)(methylcyclopentadienyl)trimethylzirconium, (13)(methylcyclopentadienyl)triphenylzirconium, (14)(methylcyclopentadienyl)tribenzylzirconium, (15)(methylcyclopentadienyl)trichlorozirconium, (16)(methylcyclopentadienyl)dimethyl(methoxy)zirconium, (17)(dimethylcyclopentadienyl)trichlorozirconium, (18)(trimethylcyclopentadienyl)trichlorozirconium, (19)(trimethylsilylcyclopentadienyl)trimethylzirconium, (20)(tetramethylcyclopentadienyl)trichlorozirconium, (21)(octahydrofluorenyl)trimethoxyzirconium, (22)(octahydrofluorenyl)zirconium trichloride and compounds obtained byreplacing zirconium in the above compounds with titanium or hafnium.

As the compound represented by general formula (I) [component (A-1)],compounds represented by general formula (I) in which the substituentson the ring represented by Cp are each independently a hydrocarbon grouphaving 1 to 20 carbon atoms and the number of the substituent is 5 suchas (1) (pentamethylcyclopentadienyl)trimethylzirconium, (2)(pentamethylcyclopentadienyl)triphenylzirconium, (3)(pentamethylcyclopentadienyl)tribenzylzirconium, (4)(pentamethylcyclopentadienyl)trichlorozirconium, (5)(pentamethylcyclopentadienyl)trimethoxyzirconium and compounds obtainedby replacing zirconium in the above compounds with titanium or hafnium,which are described above, are preferable.

Component (A-2)

Examples of the compound represented by general formula (II) [component(A-2)] include (1) bis(cyclopentadienyl)dimethylzirconium, (2)bis(cyclopentadienyl)diphenylzirconium, (3)bis(cyclopentadienyl)diethylzirconium, (4)bis(cyclopentadienyl)dibenzylzirconium, (5)bis(cyclopentadienyl)dimethoxyzirconium, (6)bis(cyclopentadienyl)dichlorozirconium, (7)bis(cyclopentadienyl)dihydridozirconium, (8)bis(cyclopentadienyl)monochloromonohydridozirconium, (9)bis(methylcyclopentadienyl)dimethylzirconium, (10)bis(methylcyclopentadienyl)dichlorozirconium, (11)bis(methylcyclopentadienyl)dibenzylzirconium, (12)bis(pentamethylcyclopentadienyl)dimethylzirconium, (13)bis(pentamethylcyclopentadienyl)dichlorozirconium, (14)bis(pentamethylcyclopentadienyl)dibenzylzirconium, (15)bis(pentamethylcyclopentadienyl)chloromethylzirconium, (16)bis(pentamethylcyclopentadienyl)hydridomethylzirconium, (17)(cyclopentadienyl)(pentamethylcyclopentadienyl)dichlorozirconium, (18)bis(n-butylcyclopentadienyl)dichlorozirconium, [(CH₃)₅C₅]₂Hf(CH₂Ph)₂,[(CH₃)₅C₅]₂Zr—(CH₂Ph)₂, [(CH₃)₅C₅]₂Hf(C₆H₄-p-CH₃)₂,[(CH₃)₅C₅]₂Zr(C₆H₄-p-CH₃)₂, [(CH₃)₅C₅]₂Hf(CH₃)₂, [(C₂H₅)₅C₅]₂Hf(CH₃)₂,[(nC₃H₇)₅C₅]₂Hf(CH₃)₂, [(nC₃H₇)₅C₅]₂Zr(CH₃)₂, [(CH₃)₅C₅]₂HfH(CH₃),[CH₃)₅C₅]₂ZrH(CH₃), [(C₂H₅)₅C₅]₂HfH(CH₃), [(C₂H₅)₅C₅]₂ZrH(CH₃),[(C₃H₇)₅C₅]₂HfH(CH₃), [(C₃H₇)₅C₅]₂ZrH(CH₃), [(CH₃)₅C₅]₂Hf(H)₂,[(CH₃)₅C₅]₂Zr(H)₂, [C₂H₅](CH₃)₄C₅]₂Hf(CH₃)₂, [(C₂H₅)(CH₃)₄C₅]₂Zr(CH₃)₂,[(nC₃H₇)(CH₃)₄—C₅]₂Hf(CH₃)₂, [(nC₃H₇)(CH₃)₄C₅]₂Zr(CH₃)₂,[(nC₄H₉)(CH₃)₄C₅]₂Hf(CH₃)₂, [(nC₄H₉)(CH₃)₄C₅]₂Zr(CH₃)₂, [(CH₃)₅C₅HfCl₂,[(CH₃)₅C₅]₂ZrCl₂, [(CH₃)₅C₅]₂HfH(Cl) and [(CH₃)₅C₅]₂ZrH(Cl).

As the compound represented by general formula (II) [component (A-2)],compounds represented by general formula (II) in which the substituentson the cyclopentadienyl group are each independently a hydrocarbon grouphaving 1 to 20 carbon atoms and the number of the substituent is 1 to 5such as (12) bis(pentamethylcyclopentadienyl)dimethylzirconium, (13)bis(pentamethylcyclopentadienyl)dichlorozirconium, (14)bis(pentamethylcyclopentadienyl)dibenzylzirconium, (15)bis(pentamethylcyclopentadienyl)chloromethylzirconium, (16)bis(pentamethylcyclopentadienyl)hydridomethylzirconium,[(CH₃)₅C₅]₂Hf(CH₂Ph)₂, [(CH₃)₅C₅]₂Zr(CH₂Ph)₂, [(CH₃)₅C₅]₂Hf(CH₃)₂,[(CH₃)₅C₅]₂HfH(CH₃), [(CH₃)₅C₅]₂ZrH(CH₃), [(CH₃)₅C₅]₂Hf(H)₂,[(CH₃)₅C₅]₂Zr(H)₂, [(C₂H₅)(CH₃)₄C₅]₂Hf(CH₃)₂, [(C₂H₅)(CH₃)₄C₅]₂Zr(CH₃)₂,[(nC₃H₇)—(CH₃)₄C₅]₂Hf(CH₃)₂, [(nC₃H₇)(CH₃)₄C₅]₂Zr(CH₃)₂,[n-C₄H₉](CH₃)₄C₅]₂—Zr(CH₃)₂, [(CH₃)₅C₅HfCl₂, [(CH₃)₅C₅]₂ZrCl₂,[(CH₃)₅C₅]₂HfH(Cl) and [(CH₃)₅C₅]₂ZrH(Cl) are preferable.

Component (A-3)

Examples of the compound represented by general formula (III) [component(A-3)] include methylenebis(indenyl)dichlorozirconium,ethylenebis(indenyl)dichlorozirconium,ethylenebis(indenyl)monochloromonohydridozirconium,ethylenebis(indenyl)chloromethylzirconium,ethylenebis(indenyl)chloromethoxyzirconium,ethylenebis(indenyl)diethoxyzirconium,ethylenebis(indenyl)dimethylzirconium,ethylenebis(4,5,6,7-tetrahydroindenyl)dichlorozirconium,ethylenebis(2-methylindenyl)dichlorozirconium,ethylenebis(2-ethylindenyl)dichlorozirconium,ethylene(2,4-dimethylcyclopentadienyl)(3′,5′-dimethylcyclopentadienyl)dichlorozirconium,ethylene(2-methyl-4-tert-butylcyclopentadienyl)(3′-tert-butyl-5′-methylcyclopentadienyl)dichlorozirconium,ethylene(2,3,5-trimethylcyclopentadienyl)(2′,4′,5′-trimethylcyclopentadienyl)dichlorozirconium,isopropylidenebis(indenyl)dichlorozirconium,isopropylidenebis(2,4-dimethylcyclopentadienyl)(3′,5′-dimethylcyclopentadienyl)dichlorozirconium,isopropylidenebis(2-methyl-4-tert-butylcyclopentadienyl)(3′-tert-butyl-5′-methylcyclopentadienyl)dichlorozirconium,isopropylidene(cyclopentadienyl)(fluorenyl)dichlorozirconium,17-cyclohexylidene(2,5-dimethylcyclopentadienyl)dichlorozirconium,dimethylsilylenebis(indenyl)dichlorozirconium,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)dichlorozirconium,dimethylsilylenebis(2-methylindenyl)dichlorozirconium,dimethylsilylenebis(2-methyl-4,5,6,7-tetrahydroindenyl)dichlorozirconium,dimethylsilylene(2,4-dimethylcyclopentadienyl)(3′,5′-dimethylcyclopentadienyl)dichlorozirconium,phenylmethylsilylenebis(indenyl)dichlorozirconium,phenylmethylsilylenbis(4,5,6,7-tetrahydroindenyl)dichlorozirconium,phenylmethylsilylene(2,4-dimethylcyclopentadienyl)(3′,5′-dimethylcyclopentadienyl)dichlorozirconium,phenylmethylsilylene(2,3,5-trimethylcyclopentadienyl)(2′,4′,5′-trimethylcyclopentadienyl)dichlorozirconium,diphenylenesilylenebis(indenyl)dichlorozirconium,tetramethyldisilylenebis(indenyl)dichlorozirconium,tetramethyldisilylenebis(3-methylcyclopentadienyl)dichlorozirconium,dicyclohexylsilylenebis(indenyl)dichlorozirconium,dicyclohexylsilylenebis(2-methylindenyl)dichlorozirconium,dicyclohexylsilylenebis-(2,4,7-trimethylindenyl)dichlorozirconium,dimethylgermaniumbis(indenyl)dichlorozirconium,dimethylgermanium(cyclopentadienyl)(fluorenyl)dichlorozirconium,methylaluminumbis(indenyl)dichlorozirconium,phenylaluminumbis(indenyl)dichlorozirconium,phenylphosphinobis(indenyl)dichlorozirconium,ethyleneboranobis(indenyl)dichlorozirconium,phenylaminobis(indenyl)dichlorozirconium andphenylamino(cyclopentadienyl)(fluorenyl)dichlorozirconium.

Further examples of the compound represented by general formula (III)include compounds described in Japanese Patent Application Laid-OpenNos. Heisei 6(1994)-184179 and Heisei 6(1994)-345809. Specific examplesof such compounds include compounds of the benzoindenyl type and theacenaphthoindenyl type such asrac-demthylsilandiylbis-1-(2-methyl-4,5-benzoindenyl)zirconiumdichloride,rac-phenylmethylsilandiylbis-1-(2-methyl-4,5-benzoindenyl)zirconiumdichloride, rac-ethandiylbis-1-(2-methyl-4,5-benzoindenyl)zirconiumdichloride, rac-butandiylbis-1-(2-methyl-4,5-benzoindenyl)zirconiumdichloride, rac-dimethylsilandiylbis-1-(4,5-benzoindenyl)zirconiumdichloride,rac-dimethylasilandiylbis-1-(2-methyl-α-methyl-α-acenaphthoindenyl)dichloride,rac-phenylmethylsilandiylbis-1-(2-methyl-α-acenaphthoindenyl)zirconiumdichloride and compounds obtained by replacing zirconium in the abovecompounds with titanium or hafnium.

Further examples of the compound represented by general formula (III)include compounds described in Japanese Patent Application Laid-OpenNos. Heisei 4(1992)-268308, Heisei 5(1993)-306304, Heisei6(1994)-100579, Heisei 6(1994)-157661, Heisei 7(1995)-149815, Heisei7(1995)-188318 and Heisei 7(1995)-258321. As the above compoundrepresented by general formula (III), compounds having hafnium as themetal represented by M¹, indenyl complexes substituted at the2-position, the 4-position or the 2,4-positions and indenyl complexeshaving hafnium as the metal represented by M¹ and substituted at the2-position, the 4-position or the 2,4-positions are preferable.

Further specific examples of the compound represented by general formula(III) include compounds substituted with an aryl group such asdimethylsilandiylbis-1-(2-methyl-4-phenylindenyl)zirconium dichloride,dimethylsilandiylbis-1-[2-methyl-4-(1-naphthyl)indenyl]zirconiumdichloride, dimethylsilandiylbis-1-(2-ethyl-4-phenylindenyl)zirconiumdichloride,dimethylsilandiylbis-1-[2-ethyl-4-(1-naphthyl)indenyl]zirconiumdichloride,phenylmethylsilandiylbis-1-(2-methyl-4-phenylindenyl)zirconiumdichloride,phenylmethylsilandiylbis-1-[2-methyl-4-(1-naphthyl)indenyl]zirconiumdichloride,phenylmethylsilandiylbis-1-(2-ethyl-4-phenylindenyl)zirconium dichlorideand phenylmethylsilandiylbis-1-[2-ethyl-4-(1-naphthyl)indenyl]zirconiumdichloride; compounds substituted at the 2,4-positions such asrac-dimethylsilylenebis-1-(2-methyl-4-ethylindenyl)zirconium dichloride,rac-dimethylsilylenebis-1-(2-methyl-4-isopropylindenyl)zirconiumdichloride,rac-dimethylsilylenebis-1-(2-methyl-4-tert-butylindenyl)zirconiumdichloride,rac-phenylmethylsilylenebis-1-(2-methyl-4-isopropylindenyl)zirconiumdichloride, rac-dimethylsilylenebis-1-(2-ethyl-4-methylindenyl)zirconiumdichloride, rac-dimethylsilylenebis-1-(2,4,-dimethylindenyl)zirconiumdichloride andrac-dimethylsilylenebis-1-(2-methyl-4-ethylindenyl)zirconium dimethyl;compounds substituted at the 4,7-positions, 2,4,7-positions or3,4,7-positions such asrac-dimethylsilylenebis-1-(4,7-dimethylindenyl)zirconium dichloride,rac-1,2-ethandiylbis-1-(2-methyl-4,7-dimethylindenyl)zirconiumdichloride, rac-dimethylsilylenebis-1-(3,4,7-trimethylindenyl)zirconiumdichloride, rac-1,2-ethandiyl-bis-1-(4,7-dimethylindenyl)zirconiumdichloride and rac-1,2-butandiylbis-1-(4,7-dimethylindenyl)zirconiumdichloride; compounds substituted at the 2,4,6-positions such asdimethylsilandiylbis-1-(2-methyl-4,6-diisopropylindenyl)-zirconiumdichloride,phenylmethylsilandiylbis-1-(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride,rac-diemthylsilandiylbis-1-(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride,rac-1,2-ethandiylbis-1-(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride,rac-diphenylsilandiylbis-1-(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride,rac-phenylmethylsilandiylbis-1-(2-methyl-4,6-diisopropylindenyl)zirconiumdichloride andrac-dimethylsilandiylbis-1-(2,4,6-trimethylindenyl)zirconium dichloride;compounds substituted at the 2,5,6-positions such asrac-dimethylsilandiylbis-1-(2,5,6-trimethylindenyl)zirconium dichloride;4,5,6,7-tetrahydroindenyl compounds such asrac-dimethysilylenbis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumchloride,rac-ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride,rac-dimethylsilylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumdimethyl,rac-ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumdimethyl,rac-ethylenebis(4,7-dimethyl-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride; and compounds obtained by replacing zirconium in the abovecompounds with titanium or hafnium.

As the compound represented by general formula (III), compoundsrepresented by the following general formula (III-a) are preferable:

In the above general formula (III-a), M¹ represents titanium atom,zirconium atom or hafnium atom. R⁷ to R¹⁷, X³ and X⁴ each independentlyrepresent hydrogen atom, a halogen atom, a hydrocarbon group having 1 to20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms andhalogen atoms, a group having silicon atom, a group having oxygen atom,a group having sulfur atom or a group having phosphorus atom. The groupsrepresented by R⁹ and R¹⁰ and the groups represented by R¹⁴ and R¹⁵ eachmay be bonded to each other and form a ring. X³ and X⁴ eachindependently represent a halogen atom, a hydrocarbon group having 1 to20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms andhalogen atoms, a group having silicon atom, a group having oxygen atom,a group having sulfur atom or a group having phosphorus atom. Arepresents a divalent crosslinking group bonding two ligands. Thedivalent crosslinking group is a hydrocarbon group having 1 to 20 carbonatoms, a hydrocarbon group having 1 to 20 carbon atoms and halogenatoms, a group having silicon atom, a group having a germanium atom, agroup having a tin atom, —O—, —CO—, —S—, —SO₂—, —NR¹⁸—, —PR¹⁸—,—P(O)R¹⁸—, —BR¹⁸— or —AlR¹⁸—, wherein R¹⁸ represents a hydrogen atom, ahalogen atom, a hydrocarbon group having 1 to 20 carbon atoms or ahydrocarbon group having 1 to 20 carbon atoms and halogen atoms.

The above transition metal compounds are complexes of the singlecrosslinking type.

Examples of the halogen atom represented by R⁷ to R¹⁷, X³ or X⁴ in theabove general formula (III-a) include chlorine atom, bromine atom,fluorine atom and iodine atom. Examples of the hydrocarbon group having1 to 20 carbon atom represented by R⁷ to R¹⁷, X³ or X⁴ include alkylgroups such as methyl group, ethyl group, n-propyl group, isopropylgroup, n-butyl group, isobutyl group, tert-butyl group, n-hexyl groupand n-decyl group; aryl groups such as phenyl group, 1-naphthyl groupand 2-naphthyl group; and aralkyl groups such as benzyl group. Examplesof the hydrocarbon group having 1 to 20 carbon atom and halogen atomsinclude groups obtained by replacing at least one hydrogen atom in theabove hydrocarbon groups with a halogen atom such as trifluoromethylgroup. Examples of the group having silicon atom include trimethylsilylgroup and dimethyl(t-butyl)silyl group. Examples of the group havingoxygen atom include methoxyl group and ethoxyl group. Examples of thegroup having sulfur atom include thiol group and sulfonic acid group.Examples of the group having nitrogen atom include dimethylamino group.Examples of the group having phosphorus include phenylphosphine group.The groups represented by R⁹ and R¹⁰ and the groups represented by R¹⁴and R¹⁵ may be bonded to each other and form a ring such as the fluorenering. It is preferable that R¹⁰, R¹¹, R¹³, R¹⁵ and R¹⁶ representhydrogen atom. It is preferable that R⁷, R⁸, R⁹, R¹², R¹⁴ and R¹⁷ eachrepresent an alkyl group having 6 or less carbon atoms, more preferablymethyl group, ethyl group, isopropyl group or cyclohexyl group and mostpreferably isopropyl group. It is preferable that X³ and X⁴ eachrepresent a halogen atom, methyl group, ethyl group or propyl group.

Examples of the group represented by A include methylene group, ethylenegroup, ethylidene group, isopropylidene group, cyclohexylidene group,1,2-cyclohexylene group, dimethylsilylene group, tetramethyldisilylenegroup, dimethylgermylene group, methylborylidene group (CH₃—B═),methylalumylidene group (CH₃—Al═), phenylphosphylidene group (Ph-P═),phenylphosphorydene group (PhPO═), 1,2-phenylene group, vinylene group(—CH═CH—), vinylidene group (CH₂═C═), methylimide group, oxygen atom(—O—) and sulfur atom (—S—). Among these groups and atoms, methylenegroup, ethylene group, ethylidene group and isopropylidene group arepreferable for achieving the object.

M¹ represents titanium, zirconium or hafnium and preferably hafnium.

Specific examples of the transition metal compound represented bygeneral formula (III-a) include1,2-ethandiyl(1-(4,7-diisopropylindenyl))-(2-(4,7-diisopropylindenyl))hafniumdichloride,1,2-ethandiyl(9-fluorenyl)-(2-(4,7-diisopropylindenyl))hafniumdichloride, isopropylidene(1-(4,7-diisopropylindenyl))(2-(4,7-diisopropylindenyl)hafniumdichloride,1,2-ethandinyl(1-(4,7-dimethylindenyl))(2-(4,7-diisopropylindenyl))hafniumdichloride, 1,2-ethandiyl(9-fluorenyl)(2-(4,7-dimethylindenyl))hafniumdichloride, isopropylidene(1-(4,7-dimethylindenyl))(2-(4,7-diispropylindenyl))hafnium dichlorideand compounds obtained by replacing hafnium in the above compounds withzirconium or titanium. However, the transition metal compoundrepresented by general formula (III-a) is not limited to the abovecompounds.

Component (A-4)

Component (A-4) is a transition metal compound represented by thefollowing general formula (IV):

In the above general formula (IV), M² represents titanium atom,zirconium atom or hafnium atom, E¹ and E² each represent a ligandselected from cyclopentadienyl group, substituted cyclopentadienylgroups, indenyl group, substituted indenyl groups,heterocyclopentadienyl groups, substituted heterocyclopentadienylgroups, amide group, phosphide group, hydrocarbon groups and groupshaving silicon atom, E¹ and E² form crosslinking structures via groupsrepresented by A¹ and A², E¹ and E² may represent the same group ordifferent groups, X¹ represents a ligand forming a σ-bond, a pluralityof X¹ may represent the same ligand or different ligands when theplurality of X¹ are present, the ligand represented by X¹ may form acrosslinking structure in combination with another ligand represented byX¹, a ligand represented by E¹ or E² or a Lewis base represented by Y¹,Y¹ represents a Lewis base, a plurality of Y¹ may represent the sameLewis base or different Lewis bases when the plurality of Y¹ arepresent, the Lewis base represented by Y¹ may form a crosslinkingstructure in combination with another Lewis base represented by Y¹ or aligand represented by E¹, E² or X¹, A¹ and A² each represent a divalentcrosslinking group which bonds two ligands and is a hydrocarbon grouphaving 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbonatoms and halogen atoms, a group having silicon atom, a group having agermanium atom, a group having a tin atom, —O—, —CO—, —S—, —SO₂—, —Se—,—NR⁴—, —PR⁴—, —P(O)R⁴—, —BR⁴— or —AlR⁴—, q represents an integer of 1 to5 which is [(a valence of the atom represented by M²]-2] and rrepresents an integer of 0 to 3. In the above, R⁴ represents a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms ora hydrocarbon group having 1 to 20 carbon atoms and halogen atoms andatoms and groups represented by a plurality of R⁴ are the same with ordifferent from each other,

In general formula (IV), M² represents titanium atom, zirconium atom orhafnium atom and preferably zirconium atom or hafnium atom. E¹ and E²each represent a ligand selected from substituted cyclopentadienylgroups, indenyl group, substituted indenyl groups,heterocyclopentadienyl groups, substituted heterocyclopentadienylgroups, amide group (—N<), phosphide group (—P<), hydrocarbon groups[>CR—, >CR<] and groups having silicone atom [>SiR—, >Si<], wherein Rrepresents hydrogen atom, a hydrocarbon group having 1 to 20 carbonatoms or a group having a heteroatom. Crosslinking structures are formedvia groups represented by A¹ and A². The atoms or the groups representedby E¹ and E² may be the same with or different from each other. It ispreferable that E¹ and E² each represent a substituted cyclopentadienylgroup, indenyl group or a substituted indenyl group.

Examples of the ligand forming a σ-bond which is represented by X¹include halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms,alkoxyl groups having 1 to 20 carbon atoms, aryloxyl groups having 6 to20 carbon atoms, amide groups having 1 to 20 carbon atoms, groups having1 to 20 carbon atoms and silicon atom, phosphide groups having 1 to 20carbon atoms, sulfide groups having 1 to 20 carbon atoms and acyl groupshaving 1 to 20 carbon atoms. A plurality of X¹ may represent the same ordifferent ligands when the plurality of X¹ are present. The atoms andgroups represented by X¹ may form a crosslinking structure incombination with another ligand represented by X¹, a ligand representedby E¹ or E² or a Lewis base represented by Y¹.

Examples of the Lewis base represented by Y¹ include amines, ethers,phosphines and thioethers. A plurality of Y¹ may represent the sameLewis base or different Lewis bases when the plurality of Y¹ arepresent, Y¹ may form a crosslinking structure in combination withanother Lewis base represented by Y¹ or a ligand represented by E¹, E²or X¹.

It is preferable that at least one of the crosslinking groupsrepresented by A¹ and A² is a crosslinking group comprising ahydrocarbon group having at least one carbon atom. Examples of thecrosslinking group include groups represented by the following generalformula:

wherein R¹⁹ and R²⁰ each represent hydrogen atom or a hydrocarbon grouphaving 1 to 20 carbon atoms, may represent the same atom or group ordifferent atoms or groups and may be bonded to each other and form acyclic structure and p represents an integer of 1 to 4. Examples of thecrosslinking group include methylene group, ethylene group, ethylidenegroup, propylidene group, isopropylidene group, cyclohexylidene group,1,2-cyclohexylene group and vinylidene group (CH₂═C═). Among thesegroups, methylene group, ethylene group and propylidene group arepreferable. The groups represented by A¹ and A² may be the same with ordifferent from each other.

When E¹ and E² each represent a substituted cyclopentadienyl group,indenyl group or a substituted indenyl group in general formula (IV)representing the transition metal compound, the bonds formed by thecrosslinking groups A¹ and A² may be the double crosslinking of the(1,1′)(2,2′) type or the double crosslinking of the (1,2′)(2,1′) type.Among the transition metal compounds represented by general formula(IV), transition metal compounds having as the ligand abiscyclopentadienyl derivative of the double crosslinking typerepresented by the following general formula (IV-a) are preferable:

In the above general formula (IV-a), M², X¹, Y¹, A¹, A², q and r are thesame as defined above. X¹ represents a ligand of the σ-bonding type. Aplurality of ligands represented by X¹ may be the same with or differentfrom each other when the plurality of ligands represented by X¹ arepresent. The ligand represented by X¹ may form a crosslinking structurein combination with another ligand represented by X¹ or with the Lewisbase represented by Y¹. Examples of the ligand represented by X¹ includethe same ligands described as the examples of the ligand represented byX¹ in general formula (IV). Y¹ represents a Lewis base. A plurality ofligands represented by Y¹ may be the same with or different from eachother when the plurality of ligands represented by Y¹ are present. Theligand represented by Y¹ may form a crosslinking structure incombination with another Lewis base represented by Y¹ or with the ligandrepresented by X¹. Examples of the Lewis base represented by Y¹ includethe same Lewis base described as the examples of the Lewis baserepresented by Y¹ in general formula (IV). R²¹ to R²⁶ each representhydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbonatoms, a hydrocarbon group having 1 to 20 carbon atoms and halogenatoms, a group having a silicon atom or a group having a heteroatom andit is necessary that at least one of R²¹ to R²⁶ do not representhydrogen atom. The atoms or the groups represented by R²¹ to R²⁶ may bethe same with or different from each other. Adjacent groups representedby R²¹ to R²⁶ may be bonded to each other and form a ring.

In the transition metal compound having the biscyclopentadienylderivative of the double crosslinking type as the ligand, the ligand maybe any of the ligand of the (1,1′)(2,2′) double crosslinking type andthe ligand of the (1,2′)(2,1′) double crosslinking type.

Specific examples of the transition metal compound represented bygeneral formula (IV-a) include(1,1′-ethylene)(2,2′-ethylene)bis(indenyl)zirconium dichloride,(1,2′-ethylene)(2,1′-ethylene)bis(indenyl)zirconium dichloride,(1,1′-methylene)(2,2′-methylene)bis(indenyl)zirconium dichloride,(1,2′-methylene)(2,1′-methylene)bis(indenyl)zirconium dichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)bis(indenyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)bis(indenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-ethylene)bis(3-methylindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)bis(3-methylindenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-ethylene)bis(4,5-benzoindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)bis(4,5-benzoindenyl)zirconium dichloride,(1,1′-ethylene)(2,2′-ethylene)bis(4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)bis(4-isopropylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)bis(5,6-dimethylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)bis(5,6-dimethylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)bis(4,7-diisopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)bis(4,7-diisopropylindenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-ethylene)bis(4-phenylindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)bis(4-phenylindenyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-ethylene)bis(3-methyl-4-isopropylindenyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-ethylene)-bis(3-methyl-4-isopropylindenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-ethylene)bis(5,6-benzoindenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-ethylene)bis(5,6-benzoindenyl)zirconiumdichloride, (1,1′-ethylene)(2,2′-isopropylidene)bis(indenyl)zirconiumdichloride, (1,2′-ethylene)(2,1′-isopropylidene)bis(indenyl)zirconiumdichloride, (1,1′-isopropylidene)(2,2′-ethylene)bis(indenyl)zirconiumdichloride, (1,2′-methylene)(2,1′-ethylene)bis(indenyl)zirconiumdichloride, (1,1′-methylene)(2,2′-ethylene)bis(indenyl) zirconiumdichloride, (1,1′-ethylene)(2,2′-methylene)bis(indenyl)zirconiumdichloride, (1,1′-methylene)(2,2′-isopropylidene)bis(indenyl)zirconiumdichloride, (1,2′-methylene)(2,1′-isopropylidene)bis(indenyl)zirconiumdichloride, (1,1′-isopropylidene)(2,2′-methylene)bis(indenyl)zirconiumdichloride,(1,1′-methylene)(2,2′-methylene)(3-methylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)(3-methylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride,(1,1′-propylidene)(2,2′-propylidene)(3-methylcyclopentadienyl)(cyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-methylene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-ethylene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-ethylene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-isopropylidene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-methylene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-isopropylidene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-methylene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-ethylene)(2,2′-isopropylidene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-methylene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-methylene)(2,2′-isopropylidene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,1′-isopropylidene)(2,2′-isopropylidene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)bis(3-methylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-methylene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-ethylene)(2,1′-isopropylidene)bis(3,4-dimethylcyclopenadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-methylene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-methylene)(2,1′-isopropylidene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride,(1,2′-isopropylidene)(2,1′-isopropylidene)bis(3,4-dimethylcyclopentadienyl)zirconiumdichloride and compounds obtained by replacing zirconium in the abovecompounds with titanium or hafnium. As the component (A-4), two or moreof the above compounds may be used in combination.

Component (A-5)

Component (A-5) is a transition metal compound represented by thefollowing general formula (V):

In the above general formula (V), M³ represents a titanium atom, azirconium atom or a hafnium atom, Cp represents a cyclic unsaturatedhydrocarbon group, a cyclopentadienyl group, a substitutedcyclopentadienyl group, an indenyl group, a substituted indenyl group, atetrahydroindenyl group, a substituted tetrahydroindenyl group, afluorenyl group or a substituted fluorenyl group, X² represents hydrogenatom, a halogen atom, an alkyl group comprising 1 to 20 carbon atoms, anaryl group comprising 6 to 20 carbon atoms, an alkylaryl groupcomprising 6 to 20 carbon atoms, an arylalkyl group comprising 6 to 20carbon atoms or an alkoxyl group having 1 to 20 carbon atoms, Zrepresents SiR⁵ ₂, CR⁵ ₂, SiR⁵ ₂SiR⁵ ₂, CR⁵ ₂CR⁵ ₂, CR⁵ ₂CR⁵ ₂CR⁵ ₂,CR⁵═CR⁵, CR⁵ ₂SiR⁵ ₂ or GeR⁵ ₂, Y² represents —N(R⁶)—, —O—, —S— or—P(R⁶)—, and s represents a number of 1 or 2. In the above, R⁵represents an alkyl group, an aryl group, a silyl group, a halogenatedalkyl group or a halogenated aryl group each having hydrogen atom or 20or less atoms which are not hydrogen atom or a group comprising acombination of these groups, and R⁶ represents an alkyl group comprising1 to 10 carbon atoms, an aryl group comprising 6 to 10 carbon atoms or acyclic system comprising at least one group represented by R⁵ group and30 or less atoms which are not hydrogen atom.

Examples of the compound represented by the above general formula (V)include(tertiary-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethandiylzirconiumdichloride,(tertiary-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethandiyltitaniumdichloride,(methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethandiylzirconiumdichloride,(methylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethandiyltitaniumdichloride,(ethylamido)(tetramethyl-η⁵-cyclopentadienyl)methylenetitaniumdichloride,(tertiary-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride,(tertiary-butylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdibenzyl,(benzylamido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanetitaniumdichloride and(phenylphosphido)dimethyl(tetramethyl-η⁵-cyclopentadienyl)silanezirconiumdibenzyl. As component (A-5), it is preferable that M³ representstitanium. Two or more of the above compounds may be used in combinationas component (A-5).

In processes I and II of the present invention, any of components (A-1)to (A-5) is preferable for producing a polyolefin-based resincomposition comprising units of ethylene and propylene in an amountexceeding 50% by mole; components (A-1), (A-3), (A-4) and (A-5) arepreferable for producing a polyolefin-based resin composition comprisingunits of α-olefins having 4 to 20 carbon atoms in an amount exceeding50% by mole; components (A-1), (A-3), (A-4) and (A-5) are preferable forproducing a polyolefin-based resin composition comprising units ofstyrenes in an amount exceeding 50% by mole; and components (A-1),(A-2), (A-3) and (A-5) are preferable for producing a polyolefin-basedresin composition comprising units of cyclic olefins in an amountexceeding 50% by mole. Tow or more components (A-1) to (A-5) may be usedin combination.

In processes I and II of the present invention, the efficiency offormation of graft copolymers can be increased and the polyolefin-basedresin composition can be produced more effectively by using as catalystcomponent (A) a component which forms a polymer comprising vinyl groupat the chain ends in an amount of 20% by mole or more based on theentire amount of the unsaturated groups. When the amount of vinyl groupat the chain ends is less than 20% by mole based the entire amount ofthe unsaturated groups, there is the possibility that the efficiency offormation of the graft copolymer decreases. It is preferable that theamount of vinyl group at the chain ends is 25% by mole or more, morepreferably 30% by mole or more, still more preferably 40% by mole ormore and most preferably 50% by mole or more, based on the entire amountof the unsaturated groups.

As the process for forming vinyl groups at the chain ends and forminglong chain branches, it is advantageous, for example, that (i) hafniumcompounds exhibiting the excellent property of forming vinyl group atthe chain ends among the preferable examples of catalyst component (A)are used as a mixture with other transition metal compounds of titaniumor zirconium.

It is also advantageous that (ii) the polymerization is conducted underthe condition which tends to form vinyl group at the chain ends and theformed polymer having vinyl group at the chain ends is copolymerizedwith a monomer.

As for the condition which tends to form vinyl group at the chain ends,for example, ethylene or propylene is contained as the essentialcomponent in the monomers and the polymerization is conducted under alow concentration of the monomer, i.e., under a pressure of the ordinarypressure to about 0.3 MPa.

It is also advantageous that (iii) a macro monomer having vinyl group atthe chain ends is prepared in advance and directly copolymerized. In theabove processes (i) to (iii), a small amount of a polyene may becontained as long as insoluble and infusible components are not formedas byproducts.

In processes I and II of the present invention, at least one substanceselected from aluminoxanes as component (B-1), ionic compounds ascomponent (B-2) which can be converted into a cation by a reaction withthe transition metal compound and clay, clay minerals and ionexchangeable lamellar compounds as component (B-3) is used as thepromoter component (B).

Examples of the aluminoxane as component (B-1) include chainaluminoxanes represented by the following general formula (VI):

wherein R²⁷ represents a hydrocarbon group having 1 to 20 carbon atomsand preferably 1 to 12 carbon atoms such as an alkyl group, an alkenylgroup, aryl group and arylalkyl group or a halogen atom, w representsthe average degree of polymerization which is an integer, in general, inthe range of 2 to 50 and preferably in the range of 2 to 40, and theatoms or the groups represented by the plurality of R²⁷ may the samewith or different from each other; and cyclic aluminoxanes representedby the following general formula (VII):

wherein R²⁷ and w are as defined for general formula (VI).

As the process for producing the aluminoxane described above, forexample, an alkylaluminum is brought into contact with a condensationagent such as water. The process for conducting the reaction is notparticularly limited and the reaction can be conducted in accordancewith a conventional process. Examples of the process include (i) aprocess in which an organoaluminum compound is dissolved into an organicsolvent and the obtained solution is brought into contact with water,(ii) a process in which an organoaluminum compound is added to thepolymerization system in advance and water is added later, (iii) aprocess in which crystal water contained in metal salts or adsorbedwater contained in inorganic compounds and organic compounds is reactedwith an organoaluminum compound, and (iv) a process in which atetraalkyldialuminoxane is brought into reaction with a trialkylaluminumand then with water.

The aluminoxane may be insoluble or soluble in hydrocarbon solvents. Itis preferable that the aluminoxane is soluble in hydrocarbon solventsand the amount of the residual organoaluminum compounds (compounds otherthan the aluminoxane) is 10% by weight or less, more preferably 3 to 5%by weight or less and most preferably 2 to 4% by weight or less asmeasured in accordance with ¹H-NMR. It is preferable that the abovealuminoxane is used since the fraction of the aluminoxane supported on acarrier (occasionally referred to as the supported fraction) increases.Since the aluminoxane is soluble in hydrocarbon solvents, anotheradvantage is found in that the aluminoxane which is not supported can berecycled and reused. Still another advantage is found in that thealuminoxane does not require any additional treatments before the usesince the properties of the aluminoxane are stable. Still anotheradvantage is found in that the average particle diameter and thedistribution of the particle diameter (occasionally, referred to as themorphology) of the polyolefin obtained by the polymerization areimproved. When the amount of the residual organoaluminum compounds(compounds other than the aluminoxane) exceeds 10% by weight, thesupported fraction decreases and the polymerization activityoccasionally decreases.

To obtain the aluminoxane, for example, a solution containing thealuminoxane is heated under a reduced pressure and the solvent isremoved to obtain a dry product (occasionally, referred to as the dry-upprocess). In the dry-up process, it is preferable that the solvent isremoved under a reduced pressure by heating at a temperature of 80° C.or lower and more preferably 60° C. or lower.

To remove components insoluble in hydrocarbon solvents from thealuminoxane, for example, components insoluble in hydrocarbon solventsmay be spontaneously precipitated and separated by decantation. Theprecipitates may be removed by centrifugation. It is preferable that aG5 glass filter under a nitrogen stream further filters the recoveredsoluble component since the insoluble components are more thoroughlyremoved. The aluminoxane obtained as described above occasionally showsan increase in the amount of gel components with the passage of time. Itis preferable that the aluminoxane is used within 48 hours and, morepreferably, immediately after being prepared. The relative amounts ofthe aluminoxane and the hydrocarbon solvent are not particularlylimited. It is preferable that the aluminoxane is used in aconcentration such that the amount of the aluminum atom in thealuminoxane is 0.5 to 10 moles per 1 liter of the hydrocarbon solvent.

Examples of the hydrocarbon solvent used above include aromatichydrocarbons such as benzene, toluene, xylene, cumene and cymene;aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane,dodecane, hexadecane and octadecane; alicyclic hydrocarbons such ascyclopentane, cyclohexane, cyclooctane and methylcyclopentane; andpetroleum fractions such as naphtha, kerosene and light gas oil.

As component (B-2), any ionic compound can be used as long as the ioniccompound can be converted into a cation by the reaction with thetransition metal compound described above. From the standpoint ofefficiently forming the active point of the polymerization, compoundsrepresented by the following general formulae (VIII) and (IX):([L¹-R²⁸]^(h+))_(p)([Z]⁻)_(b)   (VIII)([L²]^(h+))_(a)([Z]⁻)_(b)   (IX)can be advantageously used. In the above formulae (VIII) and (IX), L²represents M⁶, R²⁹R³⁰M⁶R³¹ ₃C or R³²M⁶, L¹ represents a Lewis base, and[Z]⁻ represents a non-coordinating anion represented by [Z¹]⁻ or [Z²]⁻.[Z¹]⁻ represents an anion in which a plurality of groups are bonded toan element, i.e., [M⁴G¹G² . . . G^(f)], wherein M⁴ represents an elementof Groups 5 to 15 and preferably Groups 13 to 15 of the Periodic Table,G¹ to G^(f) each represent a halogen atom, an alkyl group having 1 to 20carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, analkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20carbon atoms, an aryloxyl group having 6 to 20 carbon atoms, analkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7to 40 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms andsubstituted with halogen atoms, an acyloxyl group having 1 to 20 carbonatoms, an organometalloid group or a hydrocarbon group having 2 to 20carbon atoms and heteroatoms. Two or more groups represented by G¹ toG^(f) may be bonded to each other and form a ring. f represents aninteger expressing [(the valence of the central metal represented byM⁴)+1]. [Z²]⁻ represents a Brφnsted acid alone which has a value of(pKa), i.e., the logarithms of the inverse of the acid dissociationconstant, of −10 or smaller, a conjugate base as a combination of aBrφnsted acid and a Lewis acid or a conjugate base generally defined asa very strong acid. A Lewis base may be coordinated. R²⁸ representshydrogen atom, an alkyl group having 1 to 20 carbon atoms or an arylgroup, an alkylaryl group or an arylalkyl group each having 6 to 20carbon atoms. R²⁹ and R³⁰ each represent cyclopentadienyl group, asubstituted cyclopentadienyl group, indenyl group or fluorenyl group.R³¹ represents an alkyl group having 1 to 20 carbon atoms, an arylgroup, an alkylaryl group or an arylalkyl group. R³² represents a ligandhaving a great ring such as tetraphenylporphyrin and phthalocyanine. hrepresents the ion value of [L¹-R²⁸] or [L²] which is an integer of 1 to3, a represents an integer of 1 or greater, and b=(h×a). The elementrepresented by M⁵ include elements of Groups 1 to 3, 11 to 13 and 17 ofthe Periodic Table. M⁶ represents an element of Groups 7 to 12 of thePeriodic-Table.

Examples of the Lewis base represented by L¹ include amines such asammonia, methylamine, aniline, dimethylamine, diethylamine,N-methylaniline, diphenylamine, N,N-dimethylaniline, trimethylamine,triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine,p-bromo-N,N-dimethylaniline and p-nitro-N,N-dimethylaniline; phosphinessuch as triethylphoshine, triphenylphosphine and diphenylphosphine;thioethers such as tetrahydrothiophene; esters such as ethyl benzoate;and nitriles such as acetonitrile and benzonitrile.

Examples of the atom and the group represented by R²⁸ include hydrogenatom, methyl group, ethyl group, benzyl group and trityl group. Examplesof the group represented by R²⁹ and R³⁰ include cyclopentadienyl group,methylcyclopentadienyl group, ethylcyclopentadienyl group andpentamethylcyclopentadienyl group. Examples of the group represented byR³¹ include phenyl group, p-tolyl group and p-methoxyphenyl group.Examples of the ligand represented by R³² include tetraphenylporphyrin,phthalocyanine, allyl and methallyl. Examples of the element representedby M⁵ include Li, Na, K, Ag, Cu, Br, I and I₈. Examples of the elementrepresented by M⁶ include Mn, Fe, Co, Ni and Zn.

Examples of the element represented by M⁴ in [Z¹]⁻, i.e., [M⁴G¹G² . . .G^(f)], include B, Al, Si, P, As and Sb and preferably B and Al.Examples of the atom and the group represented by G¹ to G^(f) includedialkylamino groups such as dimethylamino group and diethylamino group;alkoxyl groups and aryloxyl groups such as methoxyl group, ethoxylgroup, n-butoxyl group and phenoxyl group; hydrocarbon groups such asmethyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, isobutyl group, n-octyl group, n-eicosyl group, phenyl group,p-tolyl group, benzyl group, 4-t-butylphenyl group and3,5-dimethylphenyl group; halogen atoms such as fluorine atom, chlorineatom, bromine atom and iodine atom; hydrocarbon groups havingheteroatoms such as p-fluorophenyl group, 3,5-difluorophenyl group,pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenylgroup, 3,5-bis(trifluoromethyl)phenyl group andbis(trimethylsilyl)methyl group; and organometalloid groups such aspentamethylantimony group, trimethylsilyl group, trimethylgermyl group,diphenylarsine group, dicyclohexylantimony group and diphenylborongroup.

Examples of the Brφnsted acid having a value of (pKa) of −10 or smalleralone and the conjugate base as a combination of a Brφnsted acid and aLewis acid, which are non-coordinating anion and represented by [Z²]⁻,include trifluoromethanesulfonic acid anion (CF₃SO₃)⁻,bis(trifluoromethanesulfonyl)methyl anion,bis(trifluoromethanesulfonyl)benzyl anion,bis(trifluoromethanesulfonyl)amide, perchlorate anion (ClO4)⁻,trifluoroacetate anion (CF₃CO₂)⁻, hexafluoroantimony anion (SbF₆)⁻,fluorosulfonate anion (FSO₃)⁻ chlorosulfonate anion (ClSO₃)⁻,fluorosulfonate anion/antimony pentafluoride (FSO₃/SbF₅)⁻,fluorosulfonate anion/arsenic pentafluoride (FSO₃/AsF₅)⁻ andtrifluoromethanesulfonate anion/antimony pentafluoride (CF₃.SO₃/SbF₅)⁻.

Examples of the compounds as component (B-2) include triethylammoniumtetraphenylborate, tri-n-butylammonium tetraphenylborate,trimethylammonium tetraphenylborate, tetraethylammoniumtetraphenylborate, methyl(tri-n-butylammonium tetraphenylborate,benzyl(tri-n-butyl)ammonium tetraphenylborate, dimethyldiphenylammoniumtetraphenylborate, triphenyl(methyl)ammonium tetraphenylborate,trimethylanilinium tetraphenylborate, methylpyridiniumtetraphenylborate, benzylpyridinium tetraphenylborate,methyl(2-cyanopyridinium) tetraphenylborate, triethylammoniumtetrakis(pentafluorophenyl)borate, tri-n-butylammoniumtetrakis(pentafluorophenyl)borate, triphenylammoniumtetrakis(pentafluorophenyl)borate, tetra-n-butylammoniumtetrakis(pentafluorophenyl)borate, tetraethylammoniumtetrakis(pentafluorophenyl)borate, benzyl(tri-n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, methyldiphenylammoniumtetrakis(pentafluorophenyl)borate, triphenyl(methyl) ammoniumtetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, trimethylaniliniumtetrakis(pentafluorophenyl)borate, methylpyridiniumtetrakis(pentafluorophenyl)borate, benzylpyridiniumtetrakis(pentafluorophenyl)borate, methyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)borate, benzyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)borate, methyl(4-cyanopyridinium)tetrakis(pentafluorophenyl)borate, triphenylphosphoniumtetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis[bis(3,5-ditrifluoromethyl)phenyl]borate, ferrocenium tetraphenylborate,silver tetraphenylborate, trityl tetraphenylborate,tetraphenylporphyrinmanganese tetraphenylborate, ferroceniumtetrakis(pentafluorophenyl)borate, (1,1′-dimethylferrocenium)tetrakis(pentafluorophenyl)borate, decamethylferroceniumtetrakis(pentafluorophenyl)borate, silvertetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, sodiumtetrakis(pentafluorophenyl)borate, tetraphenylporphyrinmanganesetetrakis(pentafluorophenyl)borate, silver tetrafluoroborate, silverhexafluorophosphate, silver hexafluoroarsenate, silver perchlorate,silver trifluoroacetate and silver trifluoromethanesulfonate. Ascomponent (B-2), the boron compounds described above are preferable.

The ionic compound as component (B-2) that can be converted into acation by the reaction with the transition metal compound of catalystcomponent (A) may be used singly or in combination of two or more.

As the clay, the clay mineral and the ion exchangeable lamellar compoundas component (B-3), the following substances are preferable.

(i) Clay and Clay Minerals

The clay is a substance which is an aggregate of fine silicate mineralscontaining water, shows plasticity when it is mixed with a suitableamount of water and rigidity when it is dried and is sintered when it isincinerated at a high temperature. The clay mineral is the silicatemineral containing water and constitutes the main component of the clay.

(ii) Ion Exchangeable Lamellar Compound

The ion exchangeable lamellar compound is a compound having a crystalstructure in which surfaces constituted with the ionic bond are laid inparallel layers by a weak bonding force and the ions contained in thestructure can be exchanged. Some of the clay minerals are the ionexchangeable lamellar compound.

Examples of the clay mineral include phyllosilicic acids. Examples ofthe phyllosilicic acids include phyllosilisic acid and phyllosilicates.Examples of the phyllosilicate include natural substances such asmontmorillonite, saponite and hectorite which belong to the group ofsmectite, illite and sericite which belong to the group of mica andmixed lamellar minerals containing minerals belonging to the groups ofsmectite and mica or minerals belonging to the groups of mica andvermiculite.

Further examples of the phyllosilicate include synthetic substances suchas fluorine tetrasilicon mica, laponite and smecton.

Further examples of the ion exchangeable lamellar compound include ioniccrystalline compounds having a lamellar crystalline structure which arenot clay minerals, such as α-Zr(HPO₄)₂, γ-Zr(HPO₄)₂, α-Ti(HPO₄)₂ andγ-Ti(HPO₄)₂.

Examples of the substance of component (B-3) which is clay or a claymineral and does not belong to the ion exchangeable lamellar compoundinclude clay called bentonite due to the small content ofmontmorillonite, Kibushi clay containing montmorillonite and many othercomponents, Gairome clay, sepiolite and palygorskite having thefiber-like form, and allophane and imogolite which are amorphous orslightly crystalline.

(iii) In processes I and II of the present invention, it is alsopreferable that component (B-3) is subjected to a chemical treatmentbefore being brought into contact with catalyst component (A),components (B-1) and (B-2) and component (C) described later from thestandpoint of the removal of impurities from the clay, the clay mineraland the ion exchangeable lamellar compound or the change in thestructure of these substances.

The chemical treatment means treatments of the surface to removeimpurities attached to the surface and treatments affecting the crystalstructure of the clay. Examples of the chemical treatment includetreatments with acids, alkalis, salts and organic substances.

By the treatment with an acid, impurities on the surface are removedand, moreover, the surface area is increased by elution of cations inthe crystal structure such as aluminum, iron and magnesium. By thetreatment with an alkali, the crystal structure of the clay is destroyedand the structure of the clay is changed. By the treatment with a saltor an organic substance, an ion complex, a molecular complex or anorganic complex is formed and the surface area and the distance betweenlayers can be changed. By utilizing the property of ion exchange,exchangeable ions between the layers are replaced with other bulky ionsand a modified lamellar substance having an increased distance betweenlayers can be obtained.

(iv) Component (B-3) described above may be used without any treatments,may be used after adsorption of water by adding water or may be usedafter dehydration by heating.

(v) Component (B-3) described above may be used after being furthertreated with an organoaluminum compound and/or an organosilane compound.

(vi) As Component (B-3), clay and clay minerals are preferable,phyllosilicic acids are more preferable, smectites are still morepreferable and montmorillonite is most preferable.

When the aluminoxane as component (B-1), the ionic compound which can beconverted into a cation by the reaction with the transition metalcompound as component (B-2) or the clay, the clay mineral or the ionexchangeable lamellar compound as component (B-3) is used as promotercomponent (B), component (B-1) may be used singly or as a combination oftwo or more types of component (B-1), component (B-2) may be used singlyor as a combination of two or more types of component (B-2), orcomponent (B-3) may be used singly or as a combination of two or moretypes of Component (B-3). A suitable combination of component (B-1) withcomponent (B-2) and component (b-3) may be used as promoter component(B).

The catalyst used in processes I and II of the present invention maycomprise an organoaluminum compound as component (C).

As the organoaluminum compound as component (C), compounds representedby the following general formula (X) is used.:R⁴⁰ _(v)AlQ_(3-v)   (X)In the above general formula (X), R⁴⁰ represents an alkyl group having 1to 10 carbon atoms, Q represents hydrogen atom, an alkoxyl group having1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or ahalogen atom, and v represents an integer of 1 to 3.

Examples of the compound represented by general formula (X) includetrimethylaluminum, triethylaluminum, triisopropylaluminum,triisobutylaluminum, dimethylaluminum chloride, diethylaluminumchloride, methylaluminum dichloride, ethylaluminum dichloride,dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminumhydride and ethylaluminum sesquichloride.

The organoaluminum compound may be used singly or in combination of twoor more.

When component (B-1) is used as the promoter component (B), it ispreferable that the ratio of the amount by mole of catalyst component(A) to the amount by mole of promoter component (B) is in the range of1:1 to 1:10⁶ and more preferably in the range of 1:10 to 1:10⁴. When theratio of the amounts is outside the above range, the cost of thecatalyst per the unit weight of the polymer increases and the amountsare not practical. When component (B-2) is used as the promotercomponent (B), it is preferable that the ratio of the amount by mole ofcatalyst component (A) to the amount by mole of promoter component (B)is in the range of 10:1 to 1:100 and more preferably in the range of1:0.5 to 1:10. When the ratio of the amounts is outside the above range,the cost of the catalyst per the unit weight of the polymer increasesand the amounts are not practical. When component (B-3) is used aspromoter component (B), it is preferable that the amount by mole ofcatalyst component (A) is in the range of 0.01×10⁻⁶ to 1×10⁻⁴ and morepreferably in the range of 0.1×10⁻⁶ to 0.5×10⁻⁴ per 1 g of component(B-3). When the amount is outside the above range, the cost of thecatalyst per the unit weight of the polymer increases and the amountsare not practical.

It is preferable that the ratio of the amount by mole of catalystcomponent (A) to the amount by mole of the organoaluminum compound ascomponent (C) which is used where desired is in the range of 1:1 to1:20,000, more preferably in the range of 1:5 to 1:2,000 and mostpreferably in the range of 1:10 to 1:1,000. The activity of the catalystper 1 g of the transition metal compound can be improved by using theorganoaluminum compound. However, when the amount of the organoaluminumis excessively great and, in particular, when the amount of theorganoaluminum compound exceeds the above range, the excess amount ofthe organoaluminum compound is not effectively used and remains in thepolymer in a great amount. An excessively small amount of theorganoaluminum compound is not preferable since the sufficient activityof the catalyst is not obtained, occasionally.

In processes I and II of the present invention, at least one of thecatalyst components may be supported on a suitable carrier. The type ofthe carrier is not particularly limited and any of carriers of inorganicoxides, other inorganic carriers and organic carriers can be used. Fromthe standpoint of the control of the morphology, carriers of inorganicoxides and other inorganic carriers are preferable.

Examples of the carrier of an inorganic oxide include SiO₂, Al₂O₃, MgO,ZrO₂, TiO₂, Fe₂O₃, B₂O₃, CaO, ZnO, BaO, ThO₂ and mixtures of thesecompounds such as silica alumina, zeolite, ferrite and glass fiber.Among these carriers, SiO₂ and Al₂O₃ are preferable. The above carriersmay comprise small amounts of carbonates, nitrates and sulfates.

Examples of the carrier other than those described above includemagnesium compounds represented by the general formula MgR⁴¹ _(x)X⁷ _(y)such as MgCl₂ and Mg(OC₂H₅)₂ and complex salts thereof. In the generalformula, R⁴¹ represents an alkyl group having 1 to 20 carbon atoms, analkoxyl group having 1 to 20 carbon atoms or an aryl group having 6 to20 carbon atoms; X⁷ represents a halogen atom or an alkyl group having 1to 20 carbon atoms; x represents a number of 0 to 2, y represents anumber of 0 to 2, and x+y=2. A plurality of the groups or the atomsrepresented by R⁴¹ or X⁷ may be the same with or different from eachother when the plurality of the groups or the atoms are present.

Examples of the organic carrier include polymers such as polystyrene,styrene-divinylbenzene copolymers, polyethylene, polypropylene andpolyarylates; starch; and carbon black.

As the carrier used in processes I and II of the present invention,MgCl₂, MgCl(OC₂H₅), Mg(OC₂H₅)₂, SiO₂ and Al₂O₃ are preferable. The formof the carrier is different depending on the type and the process ofproduction. The average diameter of the particles is, in general, in therange of 1 to 300 μm, preferably in the range of 10 to 200 μm and morepreferably in the range of 20 to 100 μm.

When the particle diameter is excessively small, fine particles in thepolymer increases. When the particle diameter is excessively great,rough grains in the polymer increases and causes a decrease in the bulkdensity and clogging in the hopper.

The specific surface area of the carrier is, in general, in the range of1 to 1,000 m²/g and preferably in the range of 50 to 500 m²/g. The porevolume is, in general, in the range of 0.1 to 5 cm³/g and preferably inthe range of 0.3 to 3 cm³/g.

When any of the specific surface area and the pore volume is outside theabove range, the activity of the catalyst occasionally decreases. Thespecific surface area and the pore volume can be obtained, for example,from the volume of the nitrogen gas adsorbed in accordance with the BETmethod (refer to J. Am. Chem. Soc., volume 60, page 309 (1983)).

When the above carrier is an inorganic carrier, it is preferable thatthe carrier is used after incineration at a temperature, in general, inthe range of 100 to 1,000° C. and preferably in the range of 130 to 800°C.

When at least one of the catalyst components is supported on the abovecarrier, it is preferable from the standpoint of the control of themorphology and the adaptation to the process such as the gas phasepolymerization that both of catalyst component (A) and promotercomponent (B) are supported.

The process for supporting at least one of catalyst component (A) andpromoter component (B) on the carrier is not particularly limited.Examples of the process include (i) a process in which at least one ofcatalyst component (A) and promoter component (B) is mixed with thecarrier; (ii) a process in which the carrier is treated with theorganoaluminum compound or the silicon compound having halogen atoms andthe treated compound is mixed with at least one of catalyst component(A) and promoter component (B); (iii) a process in which the carrier andat least one of catalyst component (A) and promoter component (B) isreacted with the organoaluminum compound or the silicon compound havinghalogen atoms; (iv) a process in which, after catalyst component (A) orpromoter component (B) is supported on, the supported component is mixedwith promoter component (B) or catalyst component (A); (v) a process inwhich a product of the catalytic reaction between catalyst component (A)and promoter component (B) is mixed with the carrier; and (vi) a processin which the catalytic reaction between catalyst component (A) andpromoter component (B) is conducted in the presence of the carrier.

The organoaluminum compound of component (C) may be added in thereaction of processes (iv) to (vi).

In processes I and II of the present invention, it is preferable thatthe ratio of the amount by weight of component (B-1) to the amount byweight of the carrier is in the range of 1:0.5 to 1:1,000 and morepreferably in the range of 1:1 to 1:50. It is preferable that the ratioof the amount by weight of component (B-2) to the amount by weight ofthe carrier is in the range of 1:5 to 1:10,000 and more preferably inthe range of 1:10 to 1:500. It is preferable that the ratio of theamount by weight of component (B-3) to the amount by weight of thecarrier is in the range of 1:0.1 to 1:2,000 and more preferably in therange of 1:0.5 to 1:1,000. When two or more types of promoter component(B) are mixed together, it is preferable that the ratio of the amount byweight of each promoter component (B) to the amount by weight of thecarrier is in the above range. It is preferable that the ratio of theamount by weight of catalyst component (A) to the amount by weight ofthe carrier is in the range of 1:5 to 1:10,000 and more preferably inthe range of 1:10 to 1:500.

When the ratio of the amount of promoter component (B) [component (B-1),component (B-1) or component (B-3)] to the amount of the carrier or theratio of the amount of catalyst component (A) to the amount of thecarrier is outside the above range, the activity of the catalystoccasionally decreases. The average particle diameter of thepolymerization catalyst prepared as described above is, in general, inthe range of 2 to 200 μm, preferably in the range of 10 to 150 μm andmore preferably in the range of 20 to 100 μm. The specific surface areais, in general, in the range of 20 to 1,000 m²/g and preferably in therange of 50 to 500 m²/g. When the average particle diameter is smallerthan 2 μm, fine particles in the polymer occasionally increase. When theparticle diameter exceeds 200 μm, rough grains in the polymeroccasionally increase. When the specific surface area is smaller than 20m²/g, the activity occasionally decreases. When the specific surfacearea exceeds 1,000 m²/g, the bulk density of the polymer occasionallydecreases. In the above polymerization catalyst, it is preferable thatthe amount of the transition metal in 100 g of the carrier is, ingeneral, in the range of 0.05 to 20 g and more preferably in the rangeof 0.1 to 10 g. When the amount of the transition metal is outside theabove range, the activity occasionally decreases. By carrying thecatalyst components on the carrier, the polyolefin-based resincomposition having the industrially advantageous bulk density and theexcellent distribution of the particle diameter can be obtained.

Catalyst component (A), promoter component (B) and, where necessary,component (C) and/or the carrier are brought into contact with eachother under an atmosphere of an inert gas in the solvent of ahydrocarbon such as pentane, hexane, heptane, toluene and cyclohexane.The temperature of the contact is in the range of −30° C. to the boilingpoint of the solvent and preferably in the range of −10 to 100° C. Thetime of the contact is, in general, in the range of 30 seconds to 10hours. After the above components are brought into contact with eachother, the solid components of the catalyst may be washed or not washed.When the above components are brought into contact with each other andtwo different transition metal compounds are used as catalyst component(A), any one of the two different transition metal compounds may be usedbefore the other or the two compounds may be used after being mixed inadvance.

The catalysts obtained as described above may be used for thepolymerization after the solvent is removed by distillation and thesolid is isolated or without any further treatments.

In processes I and II of the present invention, the catalyst can beformed by conducting the operation of supporting at least one of thecomponents (A) and (B) on the carrier in the polymerization system. Forexample, at least one of catalyst components (A) and promoter component(B), the carrier and, where necessary, the organoaluminum compound ofcomponent (C) may be added to the reaction system and the catalyst maybe obtained by preliminarily polymerizing the olefin. Examples of theolefin used for the preliminary polymerization include ethylene andα-olefins having 3 to 20 carbon atoms such as propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodeceneand 1-tetradecene. Among these olefins, a combination comprisingethylene, propylene or the α-olefin used for the copolymerization ofethylene and propylene is preferable. As the inert hydrocarbon solvent,the inert hydrocarbons described as the examples of the inerthydrocarbons used for the preparation of the solid catalyst componentscan be used. In the preliminary polymerization, the catalyst is used inan amount such that the amount of the transition metal is, in general,in the range of 10⁻⁶ to 2×10⁻² moles/liter (of the solvent) andpreferably in the range of 5×10⁻⁶ to 2×10⁻² moles/liter (of thesolvent). The ratio (Al/transition metal) of the amount by atom ofaluminum in the organoaluminum compound such as methylaluminoxane(occasionally, referred to as MAO) to the amount by atom of thetransition metal is, in general, in the range of 10 to 5,000 andpreferably in the range of 20 to 1,000. The ratio of the amount by atomof the aluminum atom in the organoaluminum compound used where necessaryto the amount by atom of the aluminum atom in MAO is, in general, in therange of 0.02 to 3 and preferably in the range of 0.05 to 1.5. The timeof the preliminary polymerization is, in general, in the range of 0.5 to100 hours and preferably in the range of about 1 to 50 hours. In thepresent invention, the catalyst obtained by preliminarily polymerizingthe olefin is preferable.

When the catalyst is prepared using the above components, it ispreferable that the operation of bringing the components into contactwith each other is conducted under the atmosphere of an inert gas suchas the nitrogen gas. The catalyst components prepared in the preparationdevice among a tank for catalyst preparation in advance may be directlyused for the copolymerization. When the catalyst is prepared in thepolymerization reactor, it is preferable that the preparation isconducted at a temperature which is the temperature of thepolymerization of an aromatic vinyl compound or lower, for example, at atemperature in the range of −30 to 200° C. and preferably in the rangeof 0 to 80° C.

It is preferable that the ratio of the amount by mole of theorganometallic compound having oxygen atom as component (B-1) to theamount by mole of the organic transition metal compound of catalystcomponent (A) is in the range of 1:0.1 to 1:100,000 and more preferablyin the range of 1:0.5 to 1:10,000. It is preferable that the ratio ofthe amount by mole of the compound as component (B-2) which forms anionic complex by the reaction with the organic transition metal compoundto the amount by mole of catalyst component (A) is in the range of 1:0.1to 1:1,000 and more preferably in the range of 1:1 to 1:100. The amountof catalyst component (A) per the unit weight (g) of the clay, the claymineral or the ion exchangeable lamellar compound as component (B-3) isin the range of 0.1 to 1,000 micromoles and preferably in the range of 1to 200 micromoles. The ratio of the amount by mole of the organometalliccompound as component (C) to the amount by mole of the organictransition metal compound of catalyst component (A) is in the range of1:1 to 1:100,000 and preferably in the range of 1:10 to 1:10,000.

The polymerization catalyst used in the present invention may be a solidcatalyst in which at least one of catalyst component (A), component(B-1), component (B-2) and component (C) is supported on fine particles.The polymerization catalyst may also be the preliminarily polymerizedcatalyst comprising the carrier of fine particles, catalyst component(A), component (B-1) (or component (B-2)), the polymer or the copolymerformed by the preliminary polymerization and, where necessary, component(C).

Process I and II of the present invention comprises the firstpolymerization stage in which at least one monomer selected fromethylene, propylene, α-olefins having 4 to 20 carbon atoms, styrenes andcyclic olefins is polymerized or copolymerized in the presence of theabove catalyst and the second polymerization stage in which thehomopolymer or the copolymer obtained in the first polymerization stageis copolymerized with at least one monomer selected from ethylene,propylene, α-olefins having 4 to 20 carbon atoms, styrenes and cyclicolefins in the presence of a polyene having at least two polymerizablecarbon-carbon double bonds in one molecule.

Examples of the α-olefin having 4 to 20 carbon atoms include α-olefinssuch as 1-butene, 3-methyl-1-butene, 4-methyl-1-butene,4-phenyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene,1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene and vinylcyclohexane; α-olefins substitutedwith halogen atoms such as hexafluoropropene, tetrafluoroethylene,2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene,trifluoroethylene and 3,4-dichloro-1-butene; and cyclic olefins such ascyclopentene, cyclohexene, cycloheptene, norbornene, 5-methylnorbornene,5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene and5-benzylnorbornene. Examples of the styrene include styrene;alkylstyrenes such as p-methylstyrene, p-ethylstyrene, p-propylstyrene,p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene,p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene,o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene,m-butylstyrene, mesitylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyreneand 3,5-dimethylstyrene; alkoxystyrenes such as p-methoxystyrene,o-methoxystyrene and m-methoxystyrene; halogenated styrenes such asp-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene,m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene,o-fluorostyrene and o-methyl-p-fluorostyrene; trimethylsilylstyrene; andesters of vinylbenzoic acid.

As the polyene used in the second polymerization stage, any polyene canbe used as long as the polyene has at least two polymerizablecarbon-carbon double bonds in one molecule. Examples of the polyeneinclude polyenes of the α,ω-type such as 1,3-butadiene, 1,4-pentadiene,1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,13-tetradecadiene,1,15-hexadecadiene, 4,4-dimethyl-1,9-decadiene,4,4-dimethyl-1,9-decadiene, 1,5,9-decatriene, 5-allyl-1,9-decadiene and1,19-eicodiene; polyenes of the styrene type such as p-divinylbenzene,m-divinylbenzene, o-divinylbenzene, di(p-vinylphenyl)methane,1,3-bis(p-vinylphenyl)propane and 1,5-bis(p-vinylphenyl)pentane; cyclicpolyenes such as 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene,5-isopropylidene-2-norbornene, dicyclopentadiene,dimethyldicyclopentadiene, diethyldicyclopentadiene, compoundsrepresented by the following general formula:

wherein n represents a number of 0, 1 or 2, examples of which includebicyclo[2.2.1]hepto-2,5-diene:

tetracyclo[4.4.01^(3.3)-1^(T,10)]-3,8-dodecadiene:

andhexacyclo[6.6.1.1^(3.8)-1^(10,13)-0^(2.7)-0^(0.14)]-4,11-heptadecadiene,

compounds represented by the following general formula:

wherein n represents a number of 0, 1 or 2 and m represents a number of1 to 11, examples of which include 5-allylbicyclo[2.2.1]hepto-2-ene:

5-(3-butenyl)bicyclo[2.2.1]hepto-2-ene:

8-vinyltetracyclo[4.4.0.1^(2.5)-1^(7.10)]-3-dodecene:

and11-vinylhexacyclo[6.6.1.1^(3.5)-1^(10.13)-0^(2.7)0.0^(9.14)]-4-heptadiene:

compounds represented by the following general formula:

wherein n represents an integer of 0 to 6, examples of which include1,1-bis(5-bicyclo[2.2.1]hepta-2-enyl)methane:

1,2-bis(5-bicyclo[2.2.1]hepta-2-enyl)ethane:

and 1,6-bis(5-bicyclo[2.2.1]hepta-2-enyl)hexane:

polyenes of the styrene/α-olefin type having the styrene residue groupand the α-olefin residue group in the same molecule such asp-(2-propenyl)styrene, m-(2-propenyl)styrene, p-(3-butenyl)styrene,m-(3-butenyl)styrene, o-(3-butenyl)styrene, p-(4-pentenyl)styrene,m-(4-pentenyl)styrene, o-(4-pentenyl)styrene, p-(5-propenyl)styrene,p-(7-octenyl)styrene, p-(1-methyl-3-butenyl)styrene,p-(2-methyl-3-butenyl)styrene, o-(2-methyl-3-butenyl)styrene,p-(3-methyl-3-butenyl)styrene, p-(2-ethyl-3-butenyl)styrene,p-(2-ethyl-4-pentenyl)styrene, p-(3-butenyl)-α-methylstyrene,m-(3-butenyl)-α-methylstyrene, o-(3-butenyl)-α-methylstyrene,4-vinyl-4′-(3-butenyl)biphenyl, 4-vinyl-3′-(3-butenyl)biphenyl,4-vinyl-4′-(4-pentenyl)biphenyl, 4-vinyl-2′-(4-pentenyl)biphenyl and4-vinyl-4′-(2-methyl-3-butenyl)biphenyl; 1,4-cyclohexadiene;1,5-cyclooctadiene; 1,5-cyclododecadiene; 4-vinylcyclohexane;1-allyl-4-isopropylidenecyclohexane; 3-allyl-cyclopentene;4-allylcyclohexene; and 1-isopropenyl-4-(4-butenyl)cyclohexane.

In processes I and II of the present invention, the polyenes of theα,ω-type, the polyenes of the styrene type, the cyclic polyenes shown bythe above formulae and the polyenes of the styrene/α-olefins type arepreferable among the above polyenes since the reactivity of thecarbon-carbon double bond is great and the amount of the residualunsaturated group which tends to decrease the heat stability duringproduction of the composition can be decreased.

In process I of the present invention, the amount of the polyene havingat least two polymerizable carbon-carbon double bonds in one molecule isin the range of 1.0×10⁻⁷ to 1.0×10⁻³ moles per 1 g of the polymer or thecopolymer obtained in the first polymerization stage.

In the case of the polyenes of the α,ω-type, the polyenes of the styrenetype and the cyclic polyenes shown by the above formulae, the amount ofthe polyene is, in general, in the range of 1.0×10⁻⁷ to 2.0×10⁻⁴ moles,preferably in the range of 2.0×10⁻⁷ to 1.0×10⁻⁴ moles, more preferablyin the range of 3.0×10⁻⁷ to 0.8×10⁻⁴ moles, still more preferably in therange of 4.0×10⁻⁷ to 0.4×10⁻⁴ moles and most preferably in the range of5.0×10⁻⁷ to 0.2×10⁻⁴ moles per 1 g of the polymer or the copolymerobtained in the first polymerization stage.

In the case of the cyclic polyenes described above other than the cyclicpolyenes shown by the above formulae, the amount of the polyene is, ingeneral, in the range of 5.0×10⁻⁷ to 1.0×10⁻³ moles, preferably in therange of 1.0×10⁻⁶ to 5.0×10⁻⁴ moles, more preferably in the range of1.5×10⁻⁶ to 4.0×10⁻⁴ moles, still more preferably in the range of2.0×10⁻⁶ to 2.0×10⁻⁴ moles and most preferably in the range of 2.5×10⁻⁶to 1.0×10⁻⁴ moles per 1 g of the polymer or the copolymer obtained inthe first polymerization stage.

In the case of the polyenes of the styrene/α-polyolefin type, the amountof the polyene is, in general, in the range of 1.0×10⁻⁷ to 1.0×10⁻³moles, preferably in the range of 2.0×10⁻⁷ to 5.0×10⁻⁴ moles, morepreferably in the range of 3.0×10⁻⁷ to 4.0×10⁻⁴ moles, still morepreferably in the range of 4.0×10⁻⁷ to 2.0×10⁻⁴ moles and mostpreferably in the range of 5.0×10⁻⁷ to 1.0×10⁻⁴ moles per 1 g of thepolymer or the copolymer obtained in the first polymerization stage.

When the amount of the polyene is excessively small, there is thepossibility that the improvement in the workability cannot be expectedin the use of the obtained polyolefin-based resin composition. When theamount of the polyene is excessively great, the control on the formationof gel becomes difficult.

In process II of the present invention, the amount of the polyene havingat least two polymerizable carbon-carbon double bond in one molecule isnot particularly limited and the polyene can be used in an amount inaccordance with the necessity. The preferable amount of the polyene isthe same as that in process I.

In process I and II of the present invention, the first polymerizationstage is a stage conducted before the second polymerization stage inwhich the polyene is used and can be conducted in accordance with aprocess including a multi-stage polymerization such as the two-stagepolymerization. In the first polymerization stage, the monomersdescribed above are used. When the homopolymer of ethylene or anethylene-based copolymer of ethylene and at least one of α-olefinshaving 3 to 20 carbon atoms, styrenes and cyclic olefins is obtained inthe first polymerization stage, it is preferable that the content of theethylene unit is in the range of 50 to 100% by mole.

When the homopolymer of propylene or a copolymer of propylene and atleast one of ethylene, α-olefins having 4 to 20 carbon atoms, styrenesand cyclic olefins is obtained in the first polymerization stage, it ispreferable that the content of the propylene unit is in the range of 50to 100% by mole. It is preferable that the stereoregularity of thepropylene sequence is syndiotactic or isotactic. When the sequence isisotactic, it is preferable that mmmm (the fraction of the meso pentad)is in the range of 40 to 99.5%. When the sequence is syndiotactic, it ispreferable that rrrr (the fraction of the racemi pentad) is in the rangeof 40 to 99.5%.

In the first polymerization stage, when the homopolymer of an α-olefinhaving 4 to 20 carbon atoms, a copolymer of different types of α-olefinshaving 4 to 20 carbon atoms or an α-olefin-based copolymer of one ofα-olefins having 4 to 20 carbon atoms with at least one of ethylene,propylene, styrenes and cyclic olefins is obtained, it is preferable thecontent of the α-olefin monomer unit is in the range of 50 to 100% bymole.

In the first polymerization stage, when the homopolymer of a styrene, acopolymer of different types of styrenes or a styrene-based copolymer ofa styrene with at least one of ethylene, propylene, α-olefins having 4to 20 carbon atoms and cyclic olefins is obtained, it is preferable thatthe content of the styrene unit is in the range of 50 to 100% by mole.The stereoregularity of the styrene sequence may be atactic,syndiotactic or isotactic. When the sequence is isotactic, it ispreferable that mmmm is in the range of 40 to 99.5%. When the sequenceis syndiotactic, it is preferable that rrrr is in the range of 40 to99.9%.

In the first polymerization stage, when the homopolymer of a cyclicolefin or a cyclic olefin-based copolymer of a cyclic olefin with atleast one of ethylene, propylene, α-olefins having 4 to 20 carbon atomsand styrenes is obtained, it is preferable that the content of thecyclic olefin unit is in the range of 50 to 100% by mole.

Examples of the polyethylene-based polymer having a content of theethylene unit in the range of 50 to 100% by mole include homopolymer ofethylene, ethylene/propylene copolymers, ethylene/1-butene copolymers,ethylene/1-hexene copolymers, ethylene/1-octene copolymers,ethylene/1-decene copolymers, ethylene/eincosene copolymers,ethylene/styrene copolymers, ethylene/p-methylstyrene copolymers,ethylene/p-phenylstyrene copolymers and ethylene/norbornene copolymers.

Examples of the polypropylene-based polymer having a content of thepropylene unit in the range of 50 to 100% by mole include isotacticpolypropylene, syndiotactic polypropylene, low stereoregularityisotactic polypropylene, propylene/ethylene copolymers,propylene/1-butene copolymers, propylene/1-hexene copolymers,propylene/1-octene copolymers, propylene/1-decene copolymers,propylene/1-eicosene copolymers, propylene/norbornene copolymers,propylene/styrene copolymers, propylene/p-methylstyrene copolymers andpropylene/p-phenylstyrene copolymers.

Examples of the poly-α-olefin-based polymer having a content of theα-olefin unit having 4 to 20 carbon atoms in the range of 50 to 100% bymole include poly-1-butene, 1-butene/ethylene copolymers,1-butene/propylene copolymers, 1-butene/1-decene copolymers,1-butene/1-eicosene copolymers, 1-butene/styrene copolymers,1-butene/norbornene copolymers, poly(4-methyl-1-pentene) and copolymersobtained by replacing 1-butene in the above polymers with4-methylpentene-1.

Examples of the polystyrene-based polymer having a content of thestyrene unit in the range of 50 to 100% by mole include isotacticpolystyrene, syndiotactic polystyrene, atactic polystyrene,styrene/ethylene copolymers, styrene/propylene copolymers,styrene/1-octene copolymers, styrene/1-decene copolymers,styrene/1-eicosene copolymers, styrene/norbornene copolymers andstyrene/p-methylstyrene copolymers.

Examples of the polynorbornene-based polymer having a content of thecyclic olefin unit in the range of 50 to 100% include polynorbornene,norbornene/ethylene copolymers, norbornene/propylene copolymers andnorbornene/styrene copolymers.

It is preferable that the polymer produced in the first polymerizationstage has long chain branches.

It is preferable that the long chain branches are derived not from abranching agent having two or more polymerizing points such as dienesbut from a macro monomer having vinyl group at the chain ends.

When the first polymerization stage is conduct using a branching agent,a great amount of gel is formed along with the formation of the longbranches. The amount of the formed gel is very great even when thebranching agent is used in a very small amount. This is not preferablesince this affects the uniformity of the dispersion adversely and therange of the improvement in the melting elasticity is narrowed.Moreover, the appearance of the molded article becomes poor and thephysical properties deteriorate.

On the other hand, since the formation of the long chain based on themacro monomer essentially forms no crosslinking components causing theformation of gel, no problems described above arise and the effect offurther improving the uniformity of the dispersion and the meltingelasticity in the second polymerization stage is exhibited.

The long chain branching derived from the macromonomer may partiallycontain long chain branching derived from a diene component.

The presence of the long chain branching can be evaluated as follows.

The polyolefin produced in the first polymerization stage and havinglong chain branches even in a small amount exhibits dependency of themelt viscosity on the shearing rate different from that of polyolefinshaving no long chain branches and the content of the long chain branchesis detected utilizing this effect.

When long chain branches are present, the dependency of the meltviscosity on the shearing rate is great. Therefore, the presence of thelong chain branches can be detected by comparing a linear polymer havingno long chain branches with the polyolefin produced in the firstpolymerization stage.

It is known that this method is affected by the molecular weightdistribution. Therefore, the polyolefin produced in the firstpolymerization stage is compared with a polymer of the same type whichhas approximately the same molecular weight distribution as measured inaccordance with GPC (the gel permeation chromatography) and has no longchain branches. In other words, the polyolefin is compared with a linearpolymer having the same type of monomer units and approximately the samecomposition of the monomer units.

The method of the evaluation is specifically described in the following.

Method of the Measurement

Apparatus: An Apparatus for Measuring the Melt Viscosity RMS800(Produced by RHEOMETRICS Company)

(i) Conditions of the Measurement

Temperature: the same as or higher than the maximum melting point or theglass transition temperature of the polyolefin in the firstpolymerization stage; in general, higher than the maximum meltingtemperature by 10 to 60° C. or higher than the maximum glass transitiontemperature by 10 to 200° C.

Strain: 15%

-   -   Angular speed: 0.01 to 300 rad/s    -   Shape of the sample: cone plate

The melt viscosity is measured under varying shearing rate (i.e., theangular speed) using the above apparatus under the above conditions.

(ii) Data Processing

The value of ω₂/10ω₁ is calculated, wherein ω₁ represents the angularspeed giving a melt viscosity of 10 Pas and ω₂ represents the angularspeed giving a melt viscosity of 103 Pas.

(iii) Comparative Sample

A polymer which has clearly no branches and has approximately the sametype of monomer units, the same composition of the monomer units in thepolymer, approximately the same ratio of the weight-average molecularweight (Mw) to the number-average molecular weight (Mn), i.e., Mw/Mn,and an approximately the same ratio of the Z-average molecular weight toMw, i.e., Mz/Mn, as those of the polymer in the first polymerizationstage, is used as the comparative sample. The molecular weights aremeasured in accordance with GPC.

“Approximately the same” means that the ratio of the measured value forthe polymer in the first polymerization stage to that for thecomparative sample, i.e., the ratio of the compositions of the monomersin the polymers, Mw, Mw/Mn or Mz/Mn [for example, (Mw of the comparativesample/Mw of the polymer in the first polymerization stage)], is in therange of 0.8 to 1.2.

From the standpoint of the sequence structure of the polymer, one of thehomopolymer, the random copolymer and the block copolymer is used as thecomparative sample and it is necessary that the sequence structures inboth polymers be approximately the same.

More specifically, it is necessary that the randomness be defined for arandom copolymer. A polymer generally recognized as a random polymer canbe used. Specifically, when a product of the monomer reactivity ratiosr¹ and r², i.e., r¹×r², obtained from the sequence analysis of a polymeris 5 or smaller, the polymer is defined as the random polymer.

A block copolymer includes a blend having almost no bonding pointsbetween blocks such as a blend of polypropylene and a propylene/ethylenecopolymer having no bonding points of the polypropylene and a true blockcopolymer having bonding points between blocks.

(iv) Evaluation

When the ratio N¹/N⁰ is in the following range, it is recognized thatlong branches are present, wherein ω₂/10ω₁ of the comparative sample isrepresented by N⁰ and ω₂/10ω₁ of the polymer in the first polymerizationstage is represented by N¹.1.05≦N ¹ /N ⁰≦80It is preferable that N¹/N⁰ is in the following range:1.07≦N ¹ /N ⁰≦80,more preferably1.09≦N ¹ /N ⁰≦70,still more preferably1.10≦N ¹ /N ⁰≦65,still more preferably1.20≦N ¹ /N ⁰≦60, andit is most preferable that N¹/N⁰ is in the following range1.50≦N ¹ /N ⁰≦55.

When N¹/N⁰ is smaller than 1.05, the effect of improving the meltingelasticity of the polyolefin-based resin composition is small. WhenN¹/N⁰ exceeds 80, the melt viscosity decreases. Therefore, a value ofN¹/N⁰ outside the above range is not preferable.

When the molecular weight of the polymer obtained in the firstpolymerization stage is defined by the intrinsic viscosity, it ispreferable that the intrinsic viscosity [η] measured in decalin as thesolvent at 135° C. is in the range of 0.1 to 10 deciliter/g, morepreferably in the range of 0.15 to 8 deciliter/g, still more preferablyin the range of 0.2 to 7 deciliter/g, still more preferably in the rangeof 0.5 to 6 deciliter/g and most preferably in the range of 0.7 to 5deciliter/g. When the intrinsic viscosity is smaller than 0.1deciliter/g, there is the possibility that the polyolefin-based resincomposition of the present invention exhibits decreased mechanicalproperties as the composition. When the intrinsic viscosity exceeds 10deciliter/g, there is the possibility that workability in molding of thecomposition deteriorates.

The molecular weight distribution of the polymer produced in the firstpolymerization stage is not particularly limited. It is preferable thatthe ratio of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn), i.e., Mw/Mn, measured inaccordance with GPC (the gel permeation chromatography) is in the rangeof 1.5 to 4 and more preferably in the range of 1.6 to 3.5.

The stereoregularity of the polymer produced in the first polymerizationstage may be any of the isotactic configuration, the syndiotacticconfiguration and the atactic configuration. It is preferable that thestereoregularity is in the range such that mmmm=40 to 99.5% in the caseof the isotactic configuration and rrrr=40 to 99.5% in the case of thesyndiotactic configuration.

The polymer may be produced in the first polymerization stage inaccordance with any of the random copolymerization, the blockcopolymerization and the graft copolymerization.

Examples of the form of the reaction in the first polymerization stageinclude the slurry polymerization, the gas phase polymerization and thebulk polymerization each using a carried catalyst, the polymerization ina homogeneous system and the solution polymerization in a heterogeneoussystem. In the case of the slurry polymerization, the gas phasepolymerization and the bulk polymerization using a supported catalyst,it is preferable that the reaction product is obtained in the form ofparticles. It is preferable that the average particle diameter in thepowder morphology (the morphology of the polymer powder formed in thefirst polymerization stage) is in the range of 50 μm to 5 mm, morepreferably in the range of 100 μm to 4.5 mm and most preferably in therange of 150 μm to 4 mm. When the average particle diameter is smallerthan 50 μm, there is the possibility that piping passageways are cloggeddue to the formation of fine powder. When the average particle diameterexceeds 5 mm, there is the possibility that rough grains increase andpiping passageways are clogged.

The bulk density of the polymer powder produced in the firstpolymerization stage is, in general, in the range of 0.1 to 0.5g/milliliter, preferably in the range of 0.15 to 0.5 g/milliliter, morepreferable in the range of 0.20 to 0.5 g/milliliter and most preferablyin the range of 0.25 to 0.48 g/milliliter. When the bulk density issmaller than 0.1 g/milliliter, there is the possibility that theproductivity of the polymer per unit volume of the reactor decreases.When the bulk density exceeds 0.5 g/milliliter, there is the possibilitythat dispersion of the polyene added in the second polymerization stageand catalyst components added where necessary into the powder decreaseand the uniform composition cannot be produced.

Examples of the polymer produced in accordance with the slurrypolymerization, the gas phase polymerization and the bulk polymerizationusing a supported catalyst in the first polymerization stage includepolystyrene, copolymers of ethylene and monomer components other thanethylene (30% by mole or less), isotactic polypropylene, syndiotacticpolypropylene and copolymers of propylene and monomer components otherthan propylene (30% by mole or less).

In the case of the polymerization in the homogeneous system, it ispreferable that the formed polymer is dissolved into the polymerizationsolvent or the monomer in the condition of the production. As thesolvent, a conventional hydrocarbon compound such as toluene,cyclohexane and decane can be used. It is sufficient that thehomogeneous system is achieved by the change in the solvent or thetemperature before the second polymerization is conducted even when theformed polymer is separated in the first polymerization stage.

Examples of the polymer produced in accordance with the polymerizationin the homogeneous system in the first polymerization stage includecopolymers of ethylene and monomer components other than ethylene (30 to99% by mole), copolymers of propylene and monomer components other thanpropylene (30 to 99% by mole), atactic polypropylene and polypropylenehaving a low stereoregularity (mmmm=40 to 80% by mole).

In the case of the polymerization in the heterogeneous system, when theformed polymer is separated out as the solid component with the progressof the polymerization reaction and the formed solid polymer iscontrolled to form particles, the process is similar to the slurrypolymerization, the gas phase polymerization and the bulk polymerizationusing the supported catalyst. Examples of the polymer produced inaccordance with the polymerization in the heterogeneous system in thefirst polymerization stage include syndiotactic polystyrene andcopolymers derived from the syndiotactic polystyrene.

In the first polymerization stage, the polymerization can be conductedat a temperature in the range of −100 to 300° C. under a pressure in therange of 0.001 to 10 MPa for the polymerization time in the range of 10seconds to 8 hours.

In the case of the slurry polymerization, the gas phase polymerizationand the bulk polymerization using the supported catalyst, thepolymerization condition is not particularly limited as long as theparticulate polymer is formed. The preferable polymerization conditionsare a temperature in the range of −100 to 120° C., a polymerizationpressure in the range of 0.001 to 10 MPa and a polymerization time inthe range of 10 seconds to 8 hours. In the case of the polymerization inthe homogeneous system, the polymerization condition is not particularlylimited as long as the homogeneous condition is maintained. Thepreferable polymerization conditions are a temperature in the range of 0to 300° C., a polymerization pressure in the range of 0.001 to 10 MPaand a polymerization time in the range of 10 seconds to 3 hours.

In processes I and II of the present invention, the secondpolymerization stage is a stage of copolymerizing a monomer containing apolyene with the polymer produced in the first polymerization stage. Inthe second polymerization stage, the polymer produced in the firstpolymerization stage is used as a sort of reactor or reaction field. Thepolymer is formed by the polymerization in the presence of the polyenein the polymer obtained in the first polymerization stage and isuniformly dispersed in the polymer obtained in the first polymerizationstage. The second polymerization stage is suitably a stage for formingIPN (the interpenetrating polymer network).

The type of the monomer which can be used in the second polymerizationstage is restricted depending on the type of the monomer used in thefirst polymerization stage. When the homogeneous polymerization isconducted in the first polymerization stage and a liquid monomer isused, the complete removal of the liquid monomer is difficult after thefirst polymerization stage is completed and, in general, the liquidmonomer is left remaining in the second polymerization stage. Therefore,the monomer used in the second polymerization stage is limited to thetype of the monomer containing the remaining liquid monomer.

Examples of the liquid monomer include styrenes, cyclic olefins andα-olefins having 5 to 20 carbon atoms.

When the system used in the first polymerization stage is thepolymerization system forming polymer particles using a supportedcatalyst or the polymer is separated as a solid component with theprogress of the polymerization reaction, it is possible that the monomeris removed in accordance with the means described in the following andthe type of the monomer used in the second polymerization stage is notlimited at all. For example, gaseous monomers such as ethylene andpropylene can be easily removed from the polymerization system byreducing the pressure. When the monomer is a liquid, the monomer can beseparated from the polymer using the technology of filtration.

As for the process for adding the polyene in the second polymerizationstage, it is important that the polyene is uniformly distributed in thepolymerization field before the polymerization starts in the secondpolymerization stage. Specifically, the polyene can be added after beingdissolved into the solvent used for the polymerization or a solventinert to the polymerization such as a hydrocarbon solvent and ahalogenated hydrocarbon solvent (the concentration: 0.01 to 5moles/liter) or after converting into a gas.

The addition of the polyene can be conducted while the polymer producedin the first polymerization stage is stirred or in accordance with thedry blending.

As for the rate of addition, it is preferable that the polyene in therange of 0.01 millimole to 4 moles per 100 g of the polymer produced inthe first polymerization stage is added within a time in the range of 1second to 1 hour.

The above operation may be conducted in accordance with the continuousprocess or the batch process. It is preferable that the product obtainedafter the addition of the polyene is kept for a time in the range of 1second to 1 hour to achieve the uniform dispersion.

In process I, the polymer composition obtained in the secondpolymerization stage is a composition comprising a desired combinationof the polymer obtained in the first polymerization stage and one of thepolymers shown in the following terms (i) to (v). In process II, thepolymer composition obtained in the second polymerization stage is acomposition comprising a desired combination of the polymer obtained inthe first polymerization stage and one of the polymers shown in thefollowing terms (i) and (iii) to (v). When the monomer used in the firstpolymerization stage is the same as the monomer used in the secondpolymerization monomer, a composition comprising a copolymer obtained bycopolymerizing the polyene to the polymer obtained in the firstpolymerization stage can be obtained.

-   (i) Ethylene-based copolymer: a copolymer of ethylene/polyene and a    copolymer of ethylene/polyene and at least one of α-olefins having 3    to 20 carbon atoms, styrenes and cyclic olefins (the content of    ethylene unit: 50 to 100% by mole).-   (ii) Propylene-based copolymer: a copolymer of propylene/polyene and    a copolymer of propylene/polyene and at least one of ethylene,    α-olefins having 4 to 20 carbon atoms, styrenes and cyclic olefins    (the content of the propylene unit: 50 to 100% by mole).

The stereoregularity of the propylene sequence may be isotactic orsyndiotactic. In the case of the isotactic sequence, mmmm=40 to 99.5%.In the case of the syndiotactic sequence, rrrr=40 to 99.5%.

-   (iii) α-Olefin-based copolymer: a copolymer of α-olefin having 4 to    20 carbon atoms/polyene, a copolymer of an α-olefin having 4 to 20    carbon atoms (a)/a polyene and an α-olefin having 4 to 20 carbon    atoms (b) [(a)≠(b)] and a copolymer of at least one of α-olefins    having 4 to 20 carbon atoms/a polyene and at least one of ethylene,    propylene, styrenes and cyclic olefins (the content of the α-olefin    unit: 50 to 100% by mole).-   (iv) Styrene-based copolymer: a copolymer of a styrene/polyene, a    copolymer of a styrene(c)/polyene and a styrene (d) [(c)≠(d)] and a    copolymer of a styrene/a polyene and at least one of ethylene,    propylene, α-olefins having 4 to 20 carbon atoms and cyclic olefins    (the content of the styrene unit: 50 to 100% by mole).

The stereoregularity of the styrene sequence may be isotactic orsyndiotactic. In the case of the isotactic sequence, mmmm=40 to 99.5%.In the case of the syndiotactic sequence, rrrr=40 to 99.5%.

{circle around (5)} Cyclic olefin-based copolymer: a copolymer of acyclic olefin/a polyene and a copolymer of a cyclic olefin/a polyene andat least one monomer selected from ethylene, propylene, α-olefins having4 to 20 carbon atoms and styrenes.

Specific examples of the polymer produced in the first polymerizationstage and the second polymerization stage are shown in Table 1.

TABLE 1 The first polymerization stage The second polymerization stagepolyethylene ethylene/polyene copolymer polyethyleneethylene/butene/polyene copolymer copolymers obtained by replacingbutene with other α-olefins ethylene/propylene copolymerethylene/polyene copolymer ethylene/butene copolymer ethylene/polyenecopolymer ethylene/hexene copolymer ethylene/polyene copolymerethylene/octene copolymer ethylene/polyene copolymer ethylene/octenecopolymer ethylene/octene/polyene copolymer etc. isotactic polypropyleneisotactic polypropylene/polyene copolymer syndiotactic polypropylenesyndiotactic polypropylene/polyene copolymer isotactic polypropyleneethylene/polyene copolymer isotactic polypropyleneethylene/butene/polyene copolymer isotactic polypropyleneethylene/octene/polyene copolymer etc. isotactic polypropylenecopolymers of cyclic polyolefins such as ethylene/norbornene/ polyenecopolymer isotactic polypropylene styrene/polyene copolymer isotacticpropylene/ethylene ethylene/polyene copolymer copolymer isotacticpropylene/octene copolymer ethylene/polyene copolymer isotacticpropylene/octene copolymer ethylene/octene/polyene copolymer etc.polybutene ethylene/norbornene/polyene copolymer syndiotacticpolystyrene styrene/polyene copolymer norbornene/ethylene copolymernorbornene/ethylene/polyene copolymer polyoctene octene/polyenecopolymer polyoctene ethylene/octene/polyene copolymer polydecenedecene/polyene copolymer polybutene ethylene/polyene copolymerpolybutene propylene/polyene copolymer poly(4-methyl-1-pentene)ethylene/polyene copolymer poly(4-methyl-1-pentene) propylene/polyenecopolymer poly(4-methyl-1-pentene) ethylene/poly(4-methyl-1-pentene)/polyene copolymer poly(3-methyl-1-butene) ethylene/polyenecopolymer poly(3-methyl-1-butene) propylene/polyene copolymerpoly(3-methyl-1-butene) ethylene/poly(3-methyl-1- butene)/polyenecopolymer poly(4-methyl-1-pentene)/ethylene ethylene/polyene copolymerpoly(4-methyl-1-pentene)/propylene propylene/polyene copolymer

In the polyolefin-based resin composition, it is preferable that thecontent of the polyene is greater than 0% and 10% by weight or smaller.When the workability in molding such as tension in melted condition isto be improved in the polyolefin-based resin composition, it ispreferable that the content of the polyene unit is 0.5% by weight orsmaller, more preferably 0.4% by weight or smaller, still morepreferably 0.3% by weight or smaller, still more preferably 0.2% byweight or smaller and most preferably 0.1% by weight or smaller. Whenthe polyolefin-based resin composition does not comprise the polyeneunit, the workability in molding is not improved. When the content ofthe polyene unit exceeds 10% by weight, there is the possibility thatthe melt fluidity of the resin decreases or gel is formed.

When the uniform composition is to be produced in the process forproducing the polyolefin-based resin composition, it is preferable thatthe content of the polyene unit is 5% by weight or smaller, morepreferably 4.5% by weight or smaller, still more preferably 4% by weightor smaller, still more preferably 3.5% by weight or smaller and mostpreferably 3% or smaller. When the polyolefin-based resin compositiondoes not comprise the polyene unit, the uniformity decreases. When thecontent of the polyene unit exceeds 10% by weight, there is thepossibility that the composition becomes infusible and the working bymelt molding is adversely affected although dispersion from theviewpoint of entanglement of the molecular chains is improved.

When the molecular weight of the polyolefin-based resin composition isdefined by the intrinsic viscosity, it is preferable that the intrinsicviscosity [η]_(T) measured in decalin as the solvent at 135° C. is inthe range of 0.5 to 15 deciliter/g, more preferably in the range of 0.6to 10 deciliter/g, still more preferably in the range of 0.7 to 8deciliter/g and most preferably in the range of 0.9 to 6 deciliter/g.When the intrinsic viscosity is smaller than 0.5 deciliter/g, there isthe possibility that the mechanical properties of the polyolefin-basedresin composition deteriorate. When the intrinsic viscosity exceeds 15deciliter/g, there is the possibility that working by molding becomesdifficult.

When the molecular weight of the polyolefin-based resin composition isdefined by the melt index (MI) that is an index for the molecular weightin the melted condition, it is preferable that MI is in the range of0.01 to 500 g/10 minutes. The conditions of the measurement of MI onvarious resins are in accordance with the conditions specified byJapanese Industrial Standard K7210, which are shown in the following.

-   (i) A resin composition comprising 50% by mole or more of the    ethylene unit: at 190° C. under a load of 21.18 N-   (ii) A resin composition comprising 50% by mole or more of the    propylene unit: at 230° C. under a load of 21.18 N-   (iii) A resin composition comprising the syndiotactic styrene    sequence: at 290° C. under a load of 21.18 N-   (iv) A resin composition comprising 50% by mole or more of the unit    of an α-olefin having 4 to 20 carbon atoms: at 230° C. under a load    of 21.18 N-   (v) A resin composition comprising 50% by mole or more of the unit    of a cyclic olefin: at 230° C. under a load of 21.18.

It is preferable that the molecular weight distribution of theolefin-based resin composition expressed by Mw/Mn measured in accordancewith GPC is in the range of 1.6 to 70 and more preferably in the rangeof 2.0 to 15.

The uniformity of the polyolefin-based resin composition can beevaluated from the condition of dispersion, the uniformity of the shapeof the dispersed particles and the change (the decrease) in the particlediameter in comparison with those of the composite system having nopolyene units in the visual or magnified observation of the surface orthe face of fracture of a melt molded article (such as a film, a sheetand an injection molded article) of the composition.

The uniformity of the composition can also be evaluated from theimprovement in the mechanical properties such as the elongation atbreak, the modulus and the yielding stress.

It is preferable that the fraction of the polymer obtained in the secondpolymerization stage based on the amount of the polyolefin-based resincomposition obtained in the entire production process is in the range of0.001 to 80% by weight. When the obtained polyolefin-based resincomposition is used without further treatments and the workability inmolding such as tension in melted condition is to be improved, it ispreferable that the fraction of the polymer obtained in the secondpolymerization stage is in the range of 0.001 to 40% by weight, morepreferably in the range of 0.005 to 35% by weight, still more preferablyin the range of 0.008 to 30% by weight, still more preferably in therange of 0.001 to 25% by weight, still more preferably in the range of0.02 to 25% by weight and most preferably in the range of 0.05 to 20% byweight. When the above fraction is smaller than 0.001% by weight, theimprovement in the workability in molding is slight. When the abovefraction exceeds 40% by weight, there is the possibility that the meltfluidity of the resin decreases.

When the polyolefin-based resin composition is used as the material forblending with other thermoplastic resins and the workability in moldingsuch as tension in melted condition is to be improved, or when thepolyolefin-based resin composition is used without further treatmentsand highly improved workability in molding is provided, it is preferablethat the fraction of the polymer obtained in the second polymerizationstage is in the following ranges.

Preferably in the range of 0.5 to 80% by weight, more preferably in therange of 1 to 80% by weight, still more preferably in the range of 2 to80% by weight, still more preferably in the range of 5 to 80% by weight,still more preferably in the range of 8 to 80% by weight, still morepreferably in the range of 10 to 70% by weight and most preferably inthe range of 16 to 70% by weight.

When the fraction of the polymer obtained in the second polymerizationstage is smaller than 0.5% by weight, remarkable improvement in theworkability in molding cannot be expected. When the fraction exceeds 80%by weight, the fluidity of the resin decreases.

When the uniform composition is to be produced in the process forproducing the polyolefin-based resin composition, it is preferable thatthe fraction of the polymer obtained in the second polymerization stageis in the range of 1 to 80% by weight, more preferably in the range of1.5 to 70% by weight, still more preferably in the range of 2.0 to 65%by weight, still more preferably in the range of 2.5 to 60% by weight,still more preferably in the range of 3.0 to 55% by weight and mostpreferably in the range of 3.5 to 50% by weight. When the fraction ofthe polymer obtained in the second polymerization stage is smaller than1% by weight, the effect of improving the physical properties producedin the first polymerization stage is slight. When the fraction exceeds80% by weight, the melt fluidity of the resin decreases.

When the molecular weight of the polymer produced in the firstpolymerization stage is defined by the intrinsic viscosity as describedabove, it is preferable that the intrinsic viscosity [η]₁ measured indecalin as the solvent at 135° C. is in the range of 0.1 to 10deciliter/g, more preferably in the range of 0.15 to 8 deciliter/g,still more preferably in the range of 0.2 to 7 deciliter/g, still morepreferably in the range of 1.5 to 6 deciliter/g and most preferably inthe range of 0.7 to 5 deciliter/g. When the intrinsic viscosity issmaller than 0.1 deciliter/g, there is the possibility that physicalproperties of the composition deteriorate. When the intrinsic viscosityexceeds 10 deciliter/g, there is the possibility that the working inmolding is difficult.

When the molecular weight of the polymer produced in the secondpolymerization stage is defined by the intrinsic viscosity [η]₁, theintrinsic viscosity [η]₂ measured in decalin as the solvent at 135° C.is, in general, in the range of 0.5 to 20 deciliter/g. When theworkability in molding of the polyolefin-based resin composition such asthe tension in melted condition is to be improved, it is necessary thatthe intrinsic viscosity [η]₂ be in the range of 1.5 to 20 deciliter/gwhich is greater than the intrinsic viscosity [η]₁ of the polyolefinproduced in the first polymerization stage and that the molecular weightof the polymer obtained in the second polymerization stage be decided inaccordance with the following method and satisfy the following generalformula.

When the molecular weight (the intrinsic viscosity) of the polyolefinobtained in the first polymerization stage is represented by [η]₁, themolecular weight of the polyolefin obtained in the second polymerizationstage is represented by [η]₂, the molecular weight of the compositionproduced through the second polymerization stage is represented by[η]_(T), and the fraction of the polymer obtained in the secondpolymerization stage in the entire composition is represented by F(0<F<1), the relation between [η]₁, [η]₂, [η]_(T) and F can be expressedas follows. Assuming that the molecular weight [η] is additive, [η]₂which cannot be actually measured is calculated from [η]₁, [η]_(T) and Fwhich can be actually measured. It is necessary that the followingrequirements be satisfied:[η]₂={[η]_(T)−[η]₁(1−F)}/F[η]₂/[η]₁=1.05˜10

It is preferable that [η]₂/[η]₁ is in the range of 1.06 to 10, morepreferably in the range of 1.07 to 10, still more preferably in therange of 1.08 to 10, still more preferably in the range of 1.09 to 10and most preferably in the range of 1.1 to 10. When [η]₂/[η]₁ is smallerthan 1.05, improvement in the workability in molding is slight. When[η]₂/[η]₁ exceeds 10, there is the possibility that melt fluidity of theresin decreases.

When the uniform composition is to be produced in the process forproducing the polyolefin-based resin composition, the molecular weightof the polymer produced in the second polymerization stage is in thesame range as that of the polymer produced in the first polymerizationstage. The preferable range of the molecular weight is also the same asthat of the polymer produced in the first polymerization stage. In thiscase, the molecular weight is less limited than the molecular weight inthe case for the improvement in the melt properties.

The form of the reaction in the second polymerization stage is decidedin accordance with the form of the reaction in the first polymerizationstage as shown in the following cases.

-   (i) When the first polymerization stage is conducted in accordance    with the slurry polymerization, the gas phase polymerization or the    bulk polymerization using a supported catalyst, the second    polymerization stage is conducted using the particulate reaction    product as the reactor.-   (ii) When the first polymerization stage is conducted in accordance    with the polymerization in the homogeneous system, the second    polymerization stage is also conducted in accordance with the    polymerization in the homogeneous system using the field of the    homogeneous system as the reaction field of the production of the    composition.-   (iii) When the first polymerization stage is conducted in accordance    with the polymerization in the heterogeneous solution system using a    homogeneous catalyst and solid particles are formed as the product,    the second polymerization stage is conducted using the formed solid    particles as the reactor.-   (iv) In other cases, when the solid polymer formed in the first    polymerization stage is transferred to the second polymerization    stage and the polymer is dissolved or made uniform in the melted    condition under the condition of the production in the second    polymerization stage, the second polymerization stage can be    conducted in a uniform polymerization field.

In cases (i) and (iii) described above, the composition can be producedwhile the dispersion in particles is maintained even when the polymerproduced in the second polymerization stage has a low melting point oris a so-called tacky component. The low melting point means, in general,a melting point of 60° C. or lower.

The conditions in general of the production of the polymer in the secondpolymerization stage is the temperature among the range of −100 to 300°C.; the polymerization pressure among the range of 0.001 to 10 MPa; andthe polymerization time among the range of 10 seconds to 8 hours.

In cases (i) and (iii) described above, the condition of the productionis not particularly limited as long as the particulate polymer can beformed. The preferable ranges are the temperature among the range of−100 to 120° C.; the polymerization pressure among the range of 0.001 to10 MPa; and the polymerization time among the range of 10 seconds to 8hours.

In cases (ii) and (iv) described above, the condition of the productionis not particularly limited as long as the uniformity is maintainedunder the condition of the polymerization. The preferable ranges are thetemperature among the range of 0 to 300° C.; the polymerization pressureamong the range of 0.001 to 10 MPa; and the polymerization time amongthe range of 10 seconds to 3 hours.

Process III for producing the polyolefin-based resin composition of thepresent invention will be described in the following.

Catalyst component (X) in the catalyst used in process III comprises atitanium trichloride-based compound as a catalyst component (X-1) or acatalyst component (X-2) comprising titanium, magnesium and a halogenatom as the essential components. As the titanium trichloride-basedcompound as catalyst component (X-1), there are many types of titaniumtrichloride-based compounds such as compounds obtained by reducing TiCl₄with hydrogen atom [TiCl₃(H)], compounds obtained by reducing TiCl₄ withtitanium metal [TiCl₃(T)], compounds obtained by reducing TiCl₄ withaluminum metal [TiCl₃(A)] and compounds obtained by reducing TiCl₄ withan organoaluminum compound [for example, TiCl₃ obtained by the reductionwith diethylaluminum chloride]. In the present invention, although theactivity of the catalyst is occasionally different depending on the typeof TiCl₃ used and the performance of the catalyst is not always thesame; any of the compounds which can be used as the TiCl₃-based catalystcomponent in the so-called Ziegler catalyst (including the Ziegler-Nattacatalyst) can be used. Therefore, it is not necessary that theTiCl₃-based catalyst component is purely TiCl₃. For example, TiCl₃(A) inwhich ⅓ mole of AlCl₃ is added, compounds into which an auxiliarycomponent such as an electron-donating compound is added after beingprepared and compounds inevitably or intentionally containing a smallamount of unreduced TiCl₄, over-reduced TiCl₃ or an oxidation product ofthe reducing agent can be used.

As the catalyst comprising titanium, magnesium and a halogen element asthe essential components of catalyst component (X-2), the catalystsdescribed in Japanese Patent Application Laid-Open Nos. Showa53(1978)-45688, Showa 54(1979)-3894, Showa 54(1979)-31092, Showa54(1979)-39483, Showa 54(1979)-94591, Showa 54(1979)-118484, Showa54(1979)-131589, Showa 58(1983)-5309, Showa 58(1983)-5310, Showa58(1983)-5311, Showa 58(1983)-8706, Showa 58(1983)-27732, Showa58(1983)-32604, Showa 58(1983)-32605, Showa 58(1983)-67703, Showa58(1983)-117206, Showa 58(1983)-127708, Showa 58(1983)-183708, Showa58(1983)-183709, Showa 59(1984)-149905, Showa 59(1984)-149906, Showa64(1989)-69608, Heisei 10(1998)-25318 and Heisei 11(1999)-269218 can beused.

In the catalyst comprising titanium, magnesium and a halogen element asthe essential components, the halogen element may be present in at leastone of a titanium compound and a magnesium compound or in anothercomponent. Examples of the titanium compound includetetraalkoxytitaniums such as tetramethoxytitanium, tetraethoxytitanium,tetra-n-propoxytitanium, tetraisopropoxytitanium,tetra-n-butoxytitanium, tetraisobutoxytitanium,tetracyclohexyloxytitanium and tetraphenoxytitanium; titaniumtetrahalides such as titanium tetrachloride, titanium tetrabromide andtitanium tetraiodide; alkoxytitanium trihalides such as methoxytitaniumtrichloride, ethoxytitanium trichloride, propoxytitanium trichloride,n-butoxytitanium trichloride and ethoxytitanium tribromide;dialkoxytitanium dihalides such as dimethoxytitanium dichloride,diethoxytitanium dichloride, diisopropoxytitanium dichloride,di-n-propoxytitanium dichloride and diethoxytitanium dibromide; andtrialkoxytitanium monohalides such as trimethoxytitanium chloride,triethoxytitanium chloride, triisopropoxytitanium chloride,tri-n-propoxytitanium chloride and tri-n-butoxytitanium chloride. Amongthese compounds, titanium compounds having many halogen atoms arepreferable and titanium tetrachloride is more preferable from thestandpoint of the polymerization activity. The titanium compound may beused singly or in combination of two or more.

Examples of the magnesium compound include alkylmagnesiums andarylmagnesiums such as dimethylmagnesium, diethylmagnesium,diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium,dioctylmagnesium, ethylbutylmagnesium, diphenylmagnesium anddicyclohexylmagnesium; alkoxymagnesiums and aryloxymagnesiums such asdiemethoxymagnesium, diethoxymagnesium, dipropoxymagnesium,dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium,diphenoxymagnesium and dicyclohexyloxymagnesium; alkylmagnesium halidesand arylmagnesium halides such as ethylmagnesium chloride,butylmagnesium chloride, hexylmagnesium chloride, isopropylmagnesiumchloride, isobutylmagnesium chloride, t-butylmagnesium chloride,phenylmagnesium bromide, benzylmagnesium chloride, ethylmagnesiumbromide, butylmagnesium bromide, phenylmagnesium chloride andbutylmagnesium iodide; alkoxymagnesium halides and aryloxy magnesiumhalides such as butoxymagnesium chloride, cyclohexyloxy-magnesiumchloride, phenoxymagnesium chloride, ethoxymagnesium bromide,butoxymagnesium bromide and ethoxymagnesium iodide; and magnesiumhalides such as magnesium chloride, magnesium bromide and magnesiumiodide.

Among these magnesium compounds, magnesium halides, alkoxymagnesiums,alkylmagnesiums and alkylmagnesium halides are preferable from thestandpoint of the polymerization activity and the stereoregularity. Theabove magnesium compound can be prepared from metallic magnesium or acompound having magnesium.

Catalyst component (X-2) may comprise (iii) an electron-donatingcompound (a) in addition to (i) the titanium compound and (ii) themagnesium compound. Examples of electron-donating compound (a) includeelectron-donating compounds having oxygen atom such as alcohols,phenols, ketones, aldehydes, carboxylic acids, malonic acid, esters oforganic acids and inorganic acids and ethers including monoethers,diethers and polyethers; and electron-donating compounds having nitrogenatom such as ammonia, amines, nitriles and isocyanates. Among thesecompounds, esters of polybasic carboxylic acids are preferable andesters of aromatic polybasic carboxylic acids are more preferable. Fromthe standpoint of the polymerization activity, monoesters and/ordiesters of aromatic dicarboxylic acids are still more preferable. It ispreferable that the organic group in the ester portion is a linear,branched or cyclic aliphatic hydrocarbon.

Specific examples include dialkyl esters of dicarboxylic acids such asphthalic acid, naphthalene-1,2-dicarboxylic acid,naphthalene-2,3-dicarboxylic acid,5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid,5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylic acid,indane-4,5-dicarboxylic acid and indane-5,6-dicarboxylic acid, in whichthe ester group has methyl group, ethyl group, n-propyl group, isopropylgroup, n-butyl group, isobutyl group, t-butyl group, n-pentyl group,1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group,1,1-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group,3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group,2-ethylbutyl group, n-hexyl group, cyclohexyl group, n-heptyl group,n-octyl group, n-nonyl group, 2-methylhexyl group, 3-methylhexyl group,4-methylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group,4-ethylhexyl group, 2-methylpentyl group, 3-methylpentyl group,2-ethylpentyl group or 3-ethylpentyl group. Among these compounds,diesters of phthalic acid are preferable and compounds in which theorganic group is a linear or branched aliphatic hydrocarbon group having4 or more carbon atoms are preferable.

Preferable specific examples include di-n-butyl phthalate, diisobutylphthalate, di-n-heptyl phthalate and diethyl phthalate. The abovecompounds may be used singly or in combination of two or more.

Catalyst component (X-2) may comprise (iv) a silicon compound inaddition to (i) the titanium compound, (ii) the magnesium compound and(iii) electron-donating compound (a). Examples of the silicon compoundinclude silicon tetrachloride, methoxytrichlorosilane,dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane,diethoxydichlorosilane, triethoxychlorosilane, propoxytrichlorosilane,dipropoxydichlorosilane and tripropoxychlorosilane. Among thesecompounds, silicon tetrachloride is preferable. The silicon compound maybe used singly or in combination of two or more.

Catalyst component (X-2) may further comprise (v) an organoaluminumcompound. As the organoaluminum compound, compounds having alkyl groups,halogen atoms, hydrogen atom and alkoxyl groups, aluminoxanes andmixtures of these compounds are preferable. Examples of theorganoaluminum compound include trialkylaluminums such astrimethylaluminum, triethylaluminum, triisopropylaluminum,triisobutylaluminum and trioctylaluminum; dialkylaluminum monochloridessuch as diethylaluminum monochloride, diisopropylaluminum monochloride,diisobutylaluminum monochloride and dioctylaluminum monochloride;alkylaluminum sesquihalides such as ethylaluminum sesquichloride; andchain aluminoxanes such as methylaluminoxane. Among these organoaluminumcompounds, trialkylaluminums having a lower alkyl group having 1 to 5carbon atoms such as trimethylaluminum, triethylaluminum,tripropylaluminum and triisobutylaluminum are preferable. Theorganoaluminum compound may be used singly or in combination of two ormore.

Catalyst component (X-2) may further comprise (vi) electron-donatingcompound (b). As electron-donating compound (b), organosilicon compoundshaving the Si—O—C bond, compounds having nitrogen atom, compounds havingphosphorus atom and compounds having oxygen atom can be used. Amongthese compounds, the organosilicon compounds having the Si—O—C bond,ethers and esters are preferable and the organosilicon compounds havingthe Si—O—C bond are more preferable from the standpoint of thepolymerization activity and the stereoregularity.

Examples of the compound having the Si—O—C bond includetetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane,triethylmethoxysilane, triethylethoxysilane,ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane,diisopropyldimethoxysilane, diisobutyldimethoxysilane,isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane,t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane,t-butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane,t-butylbutyldimethoxysilane, t-butylisobutyldimethoxysilane,t-butyl(s-butyl)dimethoxysilane, t-butylamyldimethoxysilane,t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane,t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane,t-butyldecyldimethoxysilane,t-butyl(3,3,3-trifluoromethylpropyl)dimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane,cyclohexylpropyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane,cyclohexyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane,dicyclohexyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane, diphenyldimethoxysilane,phenyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane,propyltrimethoxysilane, isopropyltrimethoxysilane,butyltrimethoxysilane, isobutyltrimethoxysilane,t-butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane,isoamyltrimethoxysilane, cyclopentyltrimethoxysilane,cyclohexyltrimethoxysilane, norbornanetrimethoxysilane,indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane,cyclopentyl(t-butoxy)dimethoxysilane,isopropyl(t-butoxy)dimethoxysilane, t-butyl(isobutoxy)dimethoxysilane,t-butyl(t-butoxy)dimethoxysilane, thexyltrimethoxysilane,thexylisopropoxydimethoxysilane, thexyl(t-butoxy)dimethoxysilane,thexylmethyldimethoxysilane, thexylethyldimethoxysilane,thexylisopropyldimethoxysilane, thexylcyclopentyldimethoxysilane,thexylmyristyldimethoxysilane, thexylcyclohexyldimethoxysilane,dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,dicyclohexyldimethoxysilane, bis(3-methylcyclopentyl)dimethoxysilane,bis(2-ethylcyclopentyl)dimethoxysilane, bis(2,3-diethylcyclopentyl)dimethoxysilane, bis(2,4-dimethylcyclopentyl)dimethoxysilane,bis(2,5-dimethylcyclopentyl)dimethoxysilane,bis(2,3,4-trimethylcyclopentyl)dimethoxysilane,bis(2,3,5-triethylcyclopentyl)dimethoxysilane,bis(2,3,5-trimethylcyclopentyl)dimethoxysilane andbis(tetramethylcyclopentyl)dimethoxysilane. The organosilicon compoundmay be used singly or in combination of two or more.

Examples of the compound having nitrogen atom include 2,6-substitutedpiperidines such as 2,6-diisopropylpiperidine,2,6-diisopropyl-4-methylpiperidine andN-methyl-2,2,6,6-tetramethylpiperidine; 2,5-substituted azolidines suchas 2,5-diisopropylazolidine and N-methyl-2,2,5,5-tetramethylazolidine;substituted methylenediamines such asN,N,N′,N′-tetramethylmethylenediamine andN,N,N′,N′-tetraethylmethylenediamine; and substituted imidazolidinessuch as 1,3-dibenzylimidazolidine and1,3-dibenzyl-2-phenylimidazolidine.

Examples of the compound having phosphorus atom include esters ofphosphorous acid such as triethyl phosphite, tri-n-propyl phosphite,triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite,diethyl n-butyl phosphite and diethyl phenyl phosphite. Examples of thecompound having oxygen atom include 2,6-substituted tetrahydrofuranssuch as 2,2,6,6,-tetramethyltetrahydrofuran and2,2,6,6-tetraethyltetrahydrofuran; and dimethoxymethane derivatives suchas 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene,9,9-dimethoxyfluorene and diphenyldimethoxymethane.

The titanium compound (i) is used in an amount, in general, in the rangeof 0.5 to 100 moles and preferably in the range of 1 to 50 moles per 1mole of magnesium in the magnesium compound (ii). When the amount of thetitanium compound (i) is outside the above range, the activity of thecatalyst is occasionally insufficient. (iii) Electron-donating compound(a) or (iv) electron-donating compound (b) is used in an amount, ingeneral, in the range of 0.01 to 10 moles and preferably in the range of0.05 to 1.0 mole per 1 mole of magnesium in the magnesium compound (ii).When the amount is outside the above range, the activity of the catalystand the stereoregularity are occasionally insufficient. When the siliconcompound (iv) is used, the amount of the silicon compound is, ingeneral, in the range of 0.001 to 100 moles and preferably in the rangeof 0.005 to 5.0 moles per 1 mole of magnesium in the magnesium compound(ii). When the amount is outside the above range, the activity of thecatalyst and the stereoregularity are not exhibited sufficiently and theamount of fine powder in the formed polymer occasionally increases.

Examples of the process for preparing catalyst component (X-2) include(1) a process in which the titanium compound (i), the magnesium compound(ii) and (iii) electron-donating compound (a) are brought into contactwith each other at 120 to 150° C. and washed at 100 to 150° C.; (2) aprocess in which the titanium compound (i), the magnesium compound (ii),(iii) the electron-donating compound (a) and the silicon compound (iv)are brought into contact with each other at 120 to 150° C. and washed at100 to 150° C.; (3) the titanium compound (i), the magnesium compound(ii) and (iii) electron-donating compound (a) are brought into contactwith each other to obtain a solid catalyst component and (vi)electron-donating compound (b) and the organoaluminum compound (v) arebrought into contact with the solid catalyst component; and (4) aprocess in which, after the titanium compound (i), the magnesiumcompound (ii) and (iii) electron-donating compound (a) are brought intocontact with each other at 120 to 150° C. and washed at 100 to 150° C.to obtain a solid catalyst component, (vi) electron-donating compound(b) and the organoaluminum compound (v) are brought into contact withthe solid catalyst component.

Catalyst component (X-2) can also be prepared in accordance with theprocess in which ethoxymagnesium among the magnesium compounds (ii) issuspended in an alkylbenzene (vii), thereafter, titanium tetrachlorideamong the titanium compounds (i) in an amount by volume of ½ or less ofthe amount by volume of the alkylbenzene and a diester of phthalic acidamong (iii) electron-donating compounds (a) are brought into contactwith the above suspension at 80 to 135° C., the obtained solid substanceis washed with the alkylbenzene, and the obtained solid substance isreacted with titanium tetrachloride in an amount by volume of ½ or lessof the amount by volume of the alkylbenzene (the process described inJapanese Patent Application Laid-Open No. Showa 64(1989)-69608) Examplesof the alkylbenzene include toluene, xylene, ethylbenzene, propylbenzeneor trimethylbenzene.

As the organoaluminum compound (Y) in the catalyst used in process IIIof the present invention, the same compounds as those described as theexamples of the foregoing organoaluminum compound (v) can be used. Inthe preparation of the catalyst used in the present invention, wherenecessary, an electron-donating compound (Z) is used as the thirdcomponent. As the electron-donating compound (Z) as the third component,the same compounds as those described as the examples of the foregoing(vi) electron-donating compound (b) can be used.

Catalyst component (X) is used, in general, in an amount such that theamount of titanium atom is in the range of 0.00005 to 1 millimole per 1liter of the reaction volume. The organoaluminum compound (Y) is used inan amount such that the ratio of the amounts by atom ofaluminum/titanium is, in general, in the range of 1 to 1,000 andpreferably in the range of 10 to 500. When the electron-donatingcompound (Z) is used as the third component, the electron-donatingcompound (Z) as the third component is used in an amount such that theratio of the amounts by mole of the electron-donating compound (Z)/theorganoaluminum compound (Y) is, in general, in the range of 0.001 to5.0, preferably in the range of 0.01 to 2.0 and more preferably in therange of 0.05 to 1.0. When the above ratio of the amounts by mole isoutside the above range, occasionally, the activity of the catalyst andthe stereoregularity are not exhibited sufficiently. However, the ratiocan be further decreased when the preliminary polymerization isconducted.

Process III for producing a polyolefin-based resin composition of thepresent invention comprises:

-   -   in a first polymerization stage, polymerizing or copolymerizing        at least one monomer selected from ethylene, propylene and        α-olefins having 4 to 20 carbon atoms in the presence of the        above catalyst, and    -   in a second polymerization stage, copolymerizing the homopolymer        or the copolymer obtained in the first polymerization stage with        at least one monomer selected from ethylene, propylene and        α-olefins having 4 to 20 carbon atoms in the presence of a        polyene having at least two polymerizable carbon-carbon double        bonds in one molecule.

Examples of the α-olefin having 4 to 20 carbon atoms include the sameα-olefins and α-olefins substituted with halogens as those described asthe examples of the α-olefins having 4 to 20 carbon atoms in theprocesses described above.

As the polyene used in the second polymerization stage, any polyenehaving at least two polymerizable carbon-carbon double bonds in onemolecule can be used. Examples of the polyene include the same polyenesdescribed as the examples of the polyenes in processes I and II.

In process III of the present invention, the polyenes of the α,ω-type,the polyenes of the styrene type, the cyclic polyenes shown by thechemical formulae in processes I and II and the polyenes of thestyrene-α-olefin type are preferable since the reactivity of thecarbon-carbon double bond is great and the amount of the residualunsaturated group which tends to decrease the heat stability duringproduction of the composition can be decreased.

The polyenes of the α, ω-type, the polyenes of the styrene type and thecyclic polyene shown by the chemical formulae are used in an amount, ingeneral, in the range of 1.0×10⁻⁶ to 6.0×10⁻³ moles, more preferably inthe range of 2.0×10⁻⁶ to 3.0×10⁻³ moles, still more preferably in therange of 3.0×10⁻⁶ to 2.4×10⁻³ moles, still more preferably in the rangeof 4.0×10⁻⁶ to 1.2×10⁻³ moles and most preferably in the range of5.0×10⁻⁶ to 0.6×10⁻³ moles per 1 g of the polymer obtained in the firstpolymerization stage.

Cyclic polyenes other than the cyclic polyene shown by the chemicalformulae are used in an amount, in general, in the range of 5.0×10⁻⁵ to3.0×10⁻² moles, more preferably in the range of 1.0×10⁻⁵ to 1.5×10⁻²moles, still more preferably in the range of 1.5×10⁻⁵ to 1.2×10⁻² moles,still more preferably in the range of 2.0×10⁻⁵ to 0.6×10⁻² moles andmost preferably in the range of 2.5×10⁻⁵ to 0.3×10⁻² moles per 1 g ofthe polymer obtained in the first polymerization stage.

The polyenes of the styrene/α-olefin types are used in an amount, ingeneral, in the range of 1.0×10⁻⁶ to 6.0×10⁻³ moles, more preferably inthe range of 2.0×10⁻⁶ to 3.0×10⁻³ moles, still more preferably in therange of 3.0×10⁻⁶ to 2.4×10⁻³ moles, still more preferably in the rangeof 4.0×10⁻⁶ to 1.2×10⁻³ moles and most preferably in the range of5.0×10⁻⁶ to 0.6×10⁻³ moles per 1 g of the polymer obtained in the firstpolymerization stage.

When the amount of the polyene is smaller than the above range, there isthe possibility that the improvement in the workability of the obtainedpolyolefin-based resin composition cannot be expected. When the amountof the polyene is greater than the above range, suppressing theformation of gel becomes difficult.

In process III of the present invention, the first polymerization stageis the polymerization stage conducted before the second polymerizationstage using the polyene and may be conducted in accordance with amulti-stage polymerization process such as a two-stage polymerization.The monomers described above are used in the first polymerization stage.When the homopolymer of ethylene or an ethylene-based copolymer ofethylene and at least one of α-olefins having 4 to 20 carbon atoms isobtained in the first polymerization stage, it is preferable that thecontent of the ethylene unit is in the range of 50 to 100% by mole.

When the homopolymer of propylene or a propylene-based copolymer ofpropylene and at least one of ethylene and an α-olefin having 4 to 20carbon atoms are copolymerized is obtained in the first polymerizationstage, it is preferable that the content of the propylene unit is in therange of 50 to 100% by mole. It is preferable that the stereoregularityof the propylene sequence is isotactic and mmmm (the fraction of themeso pentad) is in the range of 40 to 99.5%.

In the first polymerization stage, when the homopolymer of an α-olefinhaving 4 to 20 carbon atoms, a copolymer of different types of α-olefinshaving 4 to 20 carbon atoms or an α-olefin-based copolymer of one ofα-olefins having 4 to 20 carbon atoms with at least one of ethylene andpropylene is obtained, it is preferable the content of the α-olefinmonomer unit is in the range of 50 to 100% by mole.

Examples of the polyethylene-based polymer having a content of theethylene unit in the range of 50 to 100% include homopolymer ofethylene, ethylene/propylene copolymers, ethylene/1-butene copolymers,ethylene/1-hexene copolymers, ethylene/1-octene copolymers,ethylene/1-decene copolymers and ethylene/eincosene copolymers.

Examples of the polypropylene-based polymer having a content of thepropylene unit in the range of 50 to 100% by mole include isotacticpolypropylene, propylene/ethylene copolymers, propylene/1-butenecopolymers, propylene/1-hexene copolymers, propylene/1-octenecopolymers, propylene/1-decene copolymers and propylene/1-eicosenecopolymers.

Examples of the poly-α-olefin-based polymer having a content of theα-olefin unit having 4 to 20 carbon atoms in the range of 50 to 100% bymole include poly-1-butene, 1-butene/ethylene copolymers,1-butene/propylene copolymers, 1-butene/1-decene copolymers,1-butene/1-eicosene copolymers, poly(4-methyl-1-pentene),poly(3-methyl-1-butene) and copolymers obtained by replacing 1-butene inthe above polymers with 4-methylpentene-1 or 3-methyl-1-butene.

When the molecular weight of the polymer obtained in the firstpolymerization stage is defined by the intrinsic viscosity, it ispreferable that the intrinsic viscosity [η] measured in decalin as thesolvent at 135° C. is in the range of 0.1 to 10 deciliter/g, morepreferably in the range of 0.15 to 8 deciliter/g, still more preferablyin the range of 0.2 to 7 deciliter/g, still more preferably in the rangeof 0.5 to 6 deciliter/g and most preferably in the range of 0.7 to 5deciliter/g. When the intrinsic viscosity is smaller than 0.1deciliter/g, there is the possibility that the polyolefin-based resincomposition of the present invention exhibits decreased mechanicalproperties as the composition. When the intrinsic viscosity exceeds 10deciliter/g, there is the possibility that workability in molding of thecomposition deteriorates.

The molecular weight distribution of the polymer produced in the firstpolymerization stage is not particularly limited. It is preferable thatthe ratio of the weight-average molecular weight (Mw) to thenumber-average molecular weight (Mn), i.e., Mw/Mn, measured inaccordance with GPC (the gel permeation chromatography) is in the rangeof 2.5 to 20 and more preferably in the range of 3.5 to 15.

It is preferable as described above that the stereoregularity of thepolymer produced in the first polymerization stage is the isotacticconfiguration. It is preferable that mmmm is in the range of 40 to 99.9%and more preferably in the range of 60 to 99.9% When propylene is usedas the monomer, it is preferable that mmmm=70 to 99.9%, more preferablymm=85 to 99.5%, still more preferably mmmm=90 to 99.5%, still morepreferably mmmm=93 to 99.9%, still more preferably mmmm=95 to 99.9%,still more preferably mmmm=97 to 99.9% and most preferably mmmm=97.8 to99.9%. When mmmm is smaller than 70%, the rigidity and the heatresistance as the proper properties of polypropylene are not exhibited.A value of mmmm in the range exceeding 99.9% is desirable but it istechnologically difficult to achieve the value in this range.

The polymer may be produced in the first polymerization stage inaccordance with any of the random copolymerization, the blockcopolymerization and the graft copolymerization.

Examples of the form of the reaction in the first polymerization stageinclude the slurry polymerization, the gas phase polymerization and thebulk polymerization each using a heterogeneous catalyst and thepolymerization in a homogeneous system. In the case of the slurrypolymerization, the gas phase polymerization and the bulk polymerizationusing a heterogeneous catalyst, it is preferable that the reactionproduct is obtained in the form of particles. It is preferable that theaverage diameter of powder (the polymer powder formed in the firstpolymerization stage) is in the range of 50 μm to 5 mm, more preferablyin the range of 100 μm to 4.5 mm and most preferably in the range of 150μm to 4 mm. When the average particle diameter is smaller than 50 μm,there is the possibility that piping passageways are clogged due to theformation of fine powder. When the average particle diameter exceeds 5mm, there is the possibility that rough grains increase and pipingpassageways are clogged.

The bulk density of the polymer powder produced in the firstpolymerization stage is, in general, in the range of 0.1 to 0.5g/milliliter, preferably in the range of 0.15 to 0.5 g/milliliter, morepreferably in the range of 0.20 to 0.5 g/milliliter and most preferablyin the range of 0.25 to 0.48 g/milliliter. When the bulk density issmaller than 0.1 g/milliliter, there is the possibility that theproductivity of the polymer per unit volume of the reactor decreases.When the bulk density exceeds 0.5 g/milliliter, there is the possibilitythat dispersion of the polyene added in the second polymerization stageand catalyst components added where necessary into the powder decreaseand the uniform composition cannot be produced. The bulk density ismeasured in accordance with the method of Japanese Industrial Standard K6721.

Examples of the polymer produced in accordance with the slurrypolymerization, the gas phase polymerization and the bulk polymerizationusing a heterogeneous catalyst in the first polymerization stage includepolyethylene, copolymers of ethylene and monomer components other thanethylene (30% by mole or less), isotactic polypropylene, copolymers ofpropylene and monomer components other than propylene (30% by mole orless), poly-4-methylpentene-1, poly-3-methyl-1-butene, copolymers of4-methylpentene-1 and monomer components other than 4-methylpentene-1(30% by mole or less), poly-3-methylpentene-1 and copolymers of3-methyl-1-butene and monomer components other than 3-methyl-1-butene(30% by mole or less).

In the case of the polymerization in the homogeneous system using aheterogeneous catalyst, it is preferable that the formed polymer isdissolved into the polymerization solvent or the monomer in thecondition of the production. As the solvent, a conventional hydrocarboncompound such as toluene, cyclohexane and decane can be used. It issufficient that the homogeneous system is achieved by the change in thesolvent or the temperature before the second polymerization is conductedeven when the powder is separated in the first polymerization stage.

Examples of the polymer produced in accordance with the polymerizationin the homogeneous system in the first polymerization stage includecopolymers of ethylene and monomer components other than ethylene (30 to99% by mole), copolymers of propylene and monomer components other thanpropylene (30 to 99% by mole) and polypropylene having a lowstereoregularity (mmmm=40 to 80% by mole).

In the first polymerization stage, the polymerization can be conductedat a temperature in the range of −100 to 300° C. under a pressure in therange of 0.001 to 10 MPa for the polymerization time in the range of 10seconds to 8 hours.

In the case of the slurry polymerization, the gas phase polymerizationand the bulk polymerization using the heterogeneous catalyst, thepolymerization condition is not particularly limited as long as theparticulate polymer is formed. The preferable polymerization conditionsare a temperature in the range of −100 to 120° C., a polymerizationpressure in the range of 0.001 to 10 MPa and a polymerization time inthe range of 10 seconds to 8 hours. In the case of the homogeneouspolymerization using a heterogeneous catalyst, the polymerizationcondition is not particularly limited as long as the homogeneouscondition is maintained. The preferable polymerization conditions are atemperature in the range of 0 to 300° C., a polymerization pressure inthe range of 0.001 to 10 MPa and a polymerization time in the range of10 seconds to 3 hours.

In process III of the present invention, the second polymerization stageis a stage of copolymerizing a monomer containing a polyene with thepolymer produced in the first polymerization stage. In the secondpolymerization stage, the polymer produced in the first polymerizationstage is used as a sort of reactor or reaction field. The polymer isformed by the polymerization in the presence of the polyene in thepolymer obtained in the first polymerization stage and is uniformlydispersed in the polymer obtained in the first polymerization stage. Thesecond polymerization stage is suitably a stage for forming IPN (theinterpenetrating polymer network).

The type of the monomer which can be used in the second polymerizationstage is restricted depending on the type of the monomer used in thefirst polymerization stage. When the homogeneous polymerization isconducted in the first polymerization stage and a liquid monomer is used(process (a)), the complete removal of the liquid monomer is difficultafter the first polymerization stage is completed and, in general, theliquid monomer is left remaining in the second polymerization stage.Therefore, the monomer used in the second polymerization stage islimited to the monomers containing the remaining liquid monomer.Examples of the liquid monomer include α-olefins having 5 to 20 carbonatoms.

When the system used in the first polymerization stage is thepolymerization system forming polymer particles using a heterogeneouscatalyst (process (b)), it is possible that the monomer is removed inaccordance with the means described in the following and the type of themonomer used in the second polymerization stage is not limited at all.For example, gaseous monomers such as ethylene and propylene can beeasily removed from the polymerization system by reducing the pressure.When the monomer is a liquid, the monomer can be separated from thepolymer using the technology of filtration.

In the present invention, process (b) described above is preferablesince, in general, there is restrictions for producing a polymer havinga high molecular weight from a higher α-olefin, i.e., a liquid monomer,in comparison with that from a lower α-olefin such as ethylene andpropylene and the increase in the molecular weight in the secondpolymerization stage which is necessary to achieve the object of thepresent invention is restricted.

As for the process for adding the polyene in the second polymerizationstage, it is important that the polyene is uniformly dispersed into thepolymerization field before the polymerization starts in the secondpolymerization stage. Specifically, the polyene can be added after beingdissolved into the solvent used for the polymerization or a solventinert to the polymerization such as a hydrocarbon solvent and ahalogenated hydrocarbon solvent (the concentration: 0.01 to 10moles/liter) or after converting into a gas.

The addition of the polyene can be conducted while the polymer producedin the first polymerization stage is stirred or in accordance with thedry blending.

As for the rate of addition, it is preferable that the polyene in therange of 0.01 millimole to 4 moles per 100 g of the polymer produced inthe first polymerization stage is added within a time in the range of 1second to 1 hour.

The above operation may be conducted in accordance with the continuousprocess or the batch process. It is preferable that the product obtainedafter the addition of the polyene is kept for a time in the range of 1second to 1 hour to achieve the uniform dispersion.

The polymer composition obtained in the second polymerization stage is acomposition comprising a desired combination of the polymer obtained inthe first polymerization stage and one of the polymers shown in thefollowing terms (i) to (ii). When the monomer used in the firstpolymerization stage is the same as the monomer used in the secondpolymerization monomer, a composition comprising a copolymer obtained bycopolymerizing the polyene to the polymer obtained in the firstpolymerization stage can be obtained.

-   (i) Ethylene-based copolymer: a copolymer of ethylene/polyene and a    copolymer of ethylene/polyene and at least one of α-olefins having 3    to 20 carbon atoms (the content of ethylene unit: 50 to 100% by    mole).-   (ii) Propylene-based copolymer: a copolymer of propylene/polyene and    a copolymer of propylene/polyene and at least one of ethylene,    α-olefins having 4 to 20 carbon atoms (the content of the propylene    unit: 50 to 100% by mole).

The stereoregularity of the propylene sequence is preferably isotactic,more preferably mmmm=70 to 99.5% by mole, still more preferably mmmm=80to 99.5% by mole, still more preferably mmmm=85 to 99.5% by mole, stillmore preferably mmmm=88 to 99.5% by mole, still more preferably 90 to99.5% by mole, still more preferably mmmm=95 to 99.5% by mole and mostpreferably mmmm=97.8 to 99.5% by mole. When mmmm is smaller than 70%,the rigidity and the heat resistance as the proper properties ofpolypropylene are not exhibited. A value of mmmm in the range exceeding99.9% is desirable but it is technologically difficult to achieve thevalue in this range.

-   (iii) α-Olefin-based copolymer: a copolymer of α-olefin having 4 to    20 carbon atoms/polyene copolymer, a copolymer of an α-olefin having    4 to 20 carbon atoms (a)/a polyene and α-olefin having 4 to 20    carbon atoms (b) [(a)≠(b)] and a copolymer of at least one of    α-olefins having 4 to 20 carbon atoms, a polyene and at least one of    ethylene and propylene (the content of the α-olefin unit: 50 to 100%    by mole).

Specific examples of the polymer produced in the first polymerizationstage and the second polymerization stage are shown in Table 2.

TABLE 2 The first polymerization stage The second polymerization stagepolyethylene ethylene/polyene copolymer polyethyleneethylene/propylene/polyene copolymer polyethyleneethylene/butene/polyene copolymer ethylene/propylene copolymerethylene/polyene copolymer ethylene/butene copolymer ethylene/polyenecopolymer ethylene/hexene copolymer ethylene/polyene copolymerethylene/octene copolymer ethylene/polyene copolymer ethylene/octenecopolymer ethylene/octene/polyene copolymer isotactic polypropyleneisotactic polypropylene/polyene copolymer isotactic polypropyleneethylene/polyene copolymer isotactic polypropyleneethylene/butene/polyene copolymer isotactic polypropyleneethylene/octene/polyene copolymer isotactic polypropylene/ethyleneethylene/polyene copolymer copolymer isotactic polypropylene/ethyleneisotactic polypropylene/ethylene/ copolymer polyene copolymer isotacticpolypropylene/octene ethylene/polyene copolymer copolymer isotacticpolypropylene/octene ethylene/octene/polyene copolymer copolymerpolybutene ethylene/polyene copolymer polybutene propylene/polyenecopolymer poly(4-methyl-1-pentene) ethylene/polyene copolymerpoly(4-methyl-1-pentene) propylene/polyene copolymerpoly(4-methyl-1-pentene) ethylene/poly(4-methyl-1- pentene)/polyenecopolymer poly(3-methyl-1-butene) ethylene/polyene copolymerpoly(3-methyl-1-butene) propylene/polyene copolymerpoly(3-methyl-1-butene) ethylene/poly(3-methyl-1- butene)/polyenecopolymer poly(4-methyl-1-pentene)/ ethylene/polyene copolymer ethylenepoly(4-methyl-1-pentene)/ propylene/polyene copolymer propylene

Among the above examples, copolymers obtained by using ethylene orpropylene as the monomer in the second polymerization stage arepreferable and ethylene/polyene copolymers and propylene/polyenecopolymers are more preferable.

The content of the polyene unit in the polymer prepared in the secondpolymerization stage exceeds 0 and is 50% by weight or smaller,preferably 20% by weight or smaller, more preferably 20% by weight orsmaller, still more preferably 10% by weight or smaller, still morepreferably 5% by weight or smaller, still more preferably 2% by weightor smaller, still more preferably 1% or smaller, still more preferably0.5% or smaller, still more preferably smaller than 0.5% by weight andmost preferably 0.05% by weight.

When the content of the polyene unit exceeds 50% by weight, the meltfluidity of the resin decreases. When the content of the polyene is 0,the workability in molding is not improved.

In the above polyolefin-based resin composition, it is preferable thatthe content of the polyene unit exceeds 0 and is 10% by weight orsmaller. When the workability in molding such as tension in meltedcondition is to be improved in the polyolefin-based resin composition,it is preferable that the content of the polyene unit is 0.5% by weightor smaller, more preferably 0.4% by weight or smaller, still morepreferably 0.3% by weight or smaller, still more preferably 0.2% byweight or smaller, still more preferably 0.1% by weight or smaller andmost preferably 0.05% by weight or smaller. When the polyolefin-basedresin composition does not comprise the polyene unit, the workability inmolding is not improved. When the content of the polyene unit exceeds10% by weight, there is the possibility that the melt fluidity of theresin decreases or gel is formed.

When the uniform composition is to be produced in the process forproducing the polyolefin-based resin composition, it is preferable thatthe content of the polyene unit is 5% by weight or smaller, morepreferably 4.5% by weight or smaller, still more preferably 4% by weightor smaller, still more preferably 3.5% by weight or smaller and mostpreferably 3% or smaller. When the polyolefin-based resin compositiondoes not comprise the polyene unit, the uniformity decreases. When thecontent of the polyene unit exceeds 10% by weight, there is thepossibility that the composition becomes infusible and the working bymelt molding is adversely affected although dispersion is improved fromthe standpoint of entanglement of the molecular chains.

When the molecular weight of the polyolefin-based resin composition isdefined by the intrinsic viscosity, it is preferable that the intrinsicviscosity [η]_(T) measured in decaline as the solvent at 135° C. is inthe range of 0.5 to 15 deciliter/g, more preferably in the range of 0.6to 10 deciliter/g, still more preferably in the range of 0.7 to 8deciliter/g and most preferably in the range of 0.9 to 6 deciliter/g.When the intrinsic viscosity is smaller than 0.5 deciliter/g, there isthe possibility that the mechanical properties of the polyolefin-basedresin composition deteriorate. When the intrinsic viscosity exceeds 15deciliter/g, there is the possibility that working by molding becomesdifficult. It is necessary that the polyolefin-based resin compositiondo not contain insoluble components in this test [the requirement (c)for the resin composition obtained in the present invention]. Wheninsoluble components are contained, drawbacks arise in that theappearance of the molded article deteriorates due to the formation ofrough grains on the surface and that mechanical properties deterioratedue to the stress concentration.

When the molecular weight of the polyolefin-based resin composition isdefined by the melt index (MI) which is an index for the molecularweight in the melted condition, it is preferable that MI is in the rangeof 0.01 to 500 g/10 minutes. The conditions of the measurement of MI onvarious resins are shown in the following.

-   (i) A resin composition comprising 50% by mole or more of the    ethylene unit: at 190° C. under a load of 21.18 N-   (ii) A resin composition comprising 50% by mole or more of the    propylene unit: at 230° C. under a load of 21.18 N-   (iii) A resin composition comprising 50% by mole or more of the unit    of an α-olefin having 4 to 20 carbon atoms: at 230° C. under a load    of 21.18 N

It is preferable that the molecular weight distribution of theolefin-based resin composition expressed by Mw/Mn measured in accordancewith GPC is in the range of 2.7 to 70 and more preferably in the rangeof 3.0 to 15.

The uniformity of the polyolefin-based resin composition can beevaluated from the condition of dispersion, the uniformity of the shapeof the dispersed particles and the decrease in the particle diameter incomparison with those of conventional melt mixtures in visual ormagnified observation of the surface or the face of fracture of a meltmolded article (such as a film, a sheet and an injection molded article)of the composition.

The uniformity of the composition can be evaluate from the improvementsin the general physical properties such as the elongation at break, themodulus and the yielding stress.

It is necessary that the fraction of the polymer obtained in the secondpolymerization stage based on the amount of the polyolefin-based resincomposition obtained in the entire production process be in the range of0.001 to 80% by weight [requirement (b) for the resin compositionobtained in accordance with the process of the present invention]. Whenthe workability in molding such as tension in melted condition of theobtained polyolefin-based resin composition is to be improved, it ispreferable that the fraction of the polymer obtained in the secondpolymerization stage is in the range of 0.001 to 40% by weight, morepreferably in the range of 0.005 to 35% by weight, still more preferablyin the range of 0.008 to 30% by weight, still more preferably in therange of 0.001 to 25% by weight, still more preferably in the range of0.02 to 25% by weight and most preferably in the range of 0.05 to 20% byweight. When the above fraction is smaller than 0.001% by weight, theimprovement in the workability in molding is slight. When the abovefraction exceeds 40% by weight, there is the possibility that the meltfluidity of the resin decreases.

When the polyolefin-based resin composition is used as a material forblending with other thermoplastic resins and the workability in moldingsuch as tension in melted condition is to be improved, or when thepolyolefin-based resin composition is used without further treatmentsand improved workability in molding is to be provided, it is preferablethat the fraction of the polymer obtained in the second polymerizationstage is in the following ranges.

Preferably in the range of 0.5 to 80% by weight, more preferably in therange of 1 to 80% by weight, still more preferably in the range of 2 to80% by weight, still more preferably in the range of 5 to 80% by weight,still more preferably in the range of 8 to 80% by weight, still morepreferably in the range of 10 to 70% by weight and most preferably inthe range of 16 to 70% by weight.

When the fraction of the polymer obtained in the second polymerizationstage is less than 0.5% by weight, remarkable improvement in theworkability in molding cannot be expected. When the fraction exceeds 80%by weight, fluidity of the resin decreases.

When the uniform composition is to be produced in the process forproducing the polyolefin-based resin composition, it is preferable thatthe fraction of the polymer obtained in the second polymerization stageis in the range of 1 to 80% by weight, more preferably in the range of1.5 to 70% by weight, still more preferably in the range of 2.0 to 65%by weight, still more preferably in the range of 2.5 to 60% by weight,still more preferably in the range of 3.0 to 55% by weight and mostpreferably in the range of 3.5 to 50% by weight. When the fraction ofthe polymer obtained in the second polymerization stage is less than 1%by weight, the effect of improving the physical properties produced inthe first polymerization stage is slight. When the fraction exceeds 80%by weight, melt fluidity of the resin decreases.

As described, when the molecular weight of the polymer produced in thefirst polymerization stage is defined by the intrinsic viscosity, it ispreferable that the intrinsic viscosity [η]₁ measured in decaline as thesolvent at 135° C. is in the range of 0.1 to 10 deciliter/g, morepreferably in the range of 0.15 to 8 deciliter/g, still more preferablyin the range of 0.2 to 7 deciliter/g, still more preferably in the rangeof 1.5 to 6 deciliter/g and most preferably in the range of 0.7 to 5deciliter/g. When the intrinsic viscosity is smaller than 0.1deciliter/g, there is the possibility that physical properties of thecomposition deteriorate. When the intrinsic viscosity exceeds 10deciliter/g, there is the possibility that the working in molding isdifficult.

When the molecular weight of the polymer produced in the secondpolymerization stage is defined by the intrinsic viscosity, theintrinsic viscosity [η]₂ measured in decaline as the solvent at 135° C.is, in general, in the range of 0.5 to 20 deciliter/g. When theworkability in molding of the polyolefin-based resin composition such astension in melted condition is to be improved, it is necessary that theintrinsic viscosity [η]₂ be in the range of 1.5 to 20 deciliter/g whichis greater than the intrinsic viscosity [η]₁ of the polyolefin producedin the first polymerization stage and that the molecular weight of thepolymer obtained in the second polymerization stage be decided inaccordance with the following method and satisfy the following generalformula.

When the molecular weight (the intrinsic viscosity) of the polyolefinobtained in the first polymerization stage is represented by [η]₁, themolecular weight of the polyolefin obtained in the second polymerizationstage is represented by [η]₂, the molecular weight of the compositionproduced through the second polymerization stage is represented by[η]_(T), and the fraction of the polymer obtained in the secondpolymerization stage in the entire composition is represented by F(0<F<1), the relation between [η]₁, [η]₂, [η]_(T) and F can be expressedas follows. Assuming that the molecular weight [η] is additive, [η]₂which cannot be actually measured is calculated from [η]₁, [η]_(T) and Fwhich can be actually measured. It is necessary that the followingrequirements [requirement (a) for the resin composition obtained inaccordance with the process of the present invention] be satisfied:[η]₂={[η]_(T)−[η]₁(1−F)}/F[η]₂/[η]₁=1.05˜10

It is preferable that [η]₂/[η]₁ is in the range of 1.06 to 10, morepreferably in the range of 1.07 to 10, still more preferably in therange of 1.08 to 10, still more preferably in the range of 1.09 to 10,still more preferably in the range of 1.1 to 10 and most preferably inthe range of 2.0 to 10. When [η]₂/[η]₁ is smaller than 1.05, improvementin the workability in molding is slight. When [η]₂/[η]₁ exceeds 10,there is the possibility that melt fluidity of the resin decreases.

When the uniform composition is to be produced in the process forproducing the polyolefin-based resin composition, the molecular weightof the polymer produced in the second polymerization stage is in thesame range as that of the polymer produced in the first polymerizationstage. The preferable range of the molecular weight is also the same asthat of the polymer produced in the first polymerization stage. In thiscase, the molecular weight is less limited than the molecular weight forthe improvement in the melt properties.

The form of the reaction in the second polymerization stage is decidedin accordance with the form of the reaction in the first polymerizationstage as shown in the following cases.

-   (i) When the first polymerization stage is conducted in accordance    with the slurry polymerization, the gas phase polymerization or the    bulk polymerization using a heterogeneous catalyst, the second    polymerization stage is conducted using the particulate reaction    product as the reactor.-   (ii) When the first polymerization stage is conducted in accordance    with the polymerization in the homogeneous system using a    heterogeneous catalyst [case (1)], the second polymerization stage    is conducted in accordance with the polymerization in the    homogeneous system using the field of the homogeneous system as the    reaction field of the production of the composition.-   (iii) When the first polymerization stage is conducted in accordance    with the polymerization in the homogeneous system using a    heterogeneous catalyst [case (2)], the second polymerization stage    is conducted in accordance with the polymerization in the    homogeneous system accompanied with the formation of particulate    reaction products.-   (iv) In other cases, when the solid polymer formed in the first    polymerization stage is transferred to the second polymerization    stage and the polymer is dissolved or made uniform in the melted    condition under the condition of the production in the second    polymerization stage, the second polymerization stage can be    conducted similarly to one of cases (ii) and (iii) described above.

Among the above forms of the reaction, cases (i), (ii) and (iv) in whichparticulate products are formed in the second polymerization stage andcase (i) is more preferable.

The conditions of the production of the polymer in the secondpolymerization stage is, in general, the temperature among the range of−100 to 300° C.; the polymerization pressure among the range of 0.001 to10 MPa; and the polymerization time among the range of 10 seconds to 8hours.

When the particulate products are formed in the second polymerizationstage in cases (i), (iii) and (iv) described above, the condition of theproduction is not particularly limited as long as the particulatepolymer can be formed. The preferable ranges are: the temperature: −100to 120° C., the polymerization pressure: 0.001 to 10 MPa; and thepolymerization time: 10 seconds to 8 hours.

The polyolefins-based resin composition can be advantageously used inthe fields of the sheet molding, the extrusion expansion molding, theblow molding, the profile extrusion molding and the inflation molding.

As the two embodiments of the propylene composition of the presentinvention, polypropylene composition I and polypropylene composition IIwill be described in the following.

Polypropylene composition I will be described first.

In polypropylene composition I, the branching parameter a is in therange of:

-   -   0.35<a≦0.57        and preferably in the range of:    -   0.35<a≦0.52.

When the branching parameter a exceeds 0.57, the melt modulus of thepolypropylene composition decreases. Therefore, the property for formingcells during foaming and the resistance to draw down during blow moldingand aging of the sheet deteriorate. When the branching parameter issmaller than 0.35, the strength and the modulus of the polypropylenecomposition decrease and the properties of the obtained product becomesinferior. The value of the branching parameter a can be controlled bythe amount of the used polyene.

The branching parameter a is obtained as follows: the measurement inaccordance with GPC/MALLS (the multi-angle light scattering) isconducted; <R²>^(1/2) (the square root of the average of squares of theradii) is obtained from the slope of the intensity of the scatteredlight; the weight-average molecular weight M is obtained from theintercept of the intensity of the scattered light; <R²>^(1/2) is plottedagainst the logarithm of M; and the slope a is obtained by the method ofleast squares.

GPC/MALLS is conducted under the following condition.

Solvent: 1,2,4-trichlorobenzene Concentration: 0.3% (w/v) Temperature ofdissolution: 135° C. Apparatus for the 150C (GPC) produced by WATERSmeasurement: Company DAWN EOS ™ (multi-angle light scattering) producedby Waters Technology Company Column: Shodex UT806MLT (7.8 mmφ × 50 cm)produced by SHOWA DENKO Co., Ltd. Injection amount: 300 microliters Flowrate: 1.0 milliliter/min Increment of increase in −0.095 refractivitywith concentration (dn/dc):

In propylene composition I of the present invention, in general, thebranching index g is in the following ranges:

-   -   0.75≦g<1.0 (when the molecular weight measured in accordance        with the light scattering method is 2,000,000 to 10,000,000)    -   090≦g<1.0 (when the molecular weight measured in accordance with        the light scattering method is 500,000 to a value smaller than        2,000,000); and preferably in the following ranges:    -   0.75≦g<0.90 (when the molecular weight measured in accordance        with the light scattering method is 2,000,000 to 10,000,000)    -   092≦g<1.0 (when the molecular weight measured in accordance with        the light scattering method is 500,000 to a value smaller than        2,000,000).

By introducing the branching in the high molecular weight side havingthe molecular weight of 2,000,000 to 10,000,000, the probability ofentanglement increases and the branching effectively works even when theamount of the branching is small. In contrast, when the branching isintroduced in the low molecular weight side having the molecular weightof 500,00 to a value smaller than 2,000,000, the branching does not workeffectively since the number of the effective entanglement is small evenwhen the branching is introduced to a greater degree. When the branchingindex g is smaller than 0.75 in the case of a molecular weight of2,000,000 to 10,000,000 or the branching index g is smaller than 0.90 inthe case of a molecular weight of 500,00 to a value smaller than2,000,000, the branching points work as the entanglements and the numberof branch increases. The crosslinking takes place excessively and formsa gel and the physical properties are adversely affected. The value ofthe branching index of 1.0 means a linear high macromolecule having nobranches.

The value of g is obtained from <R²>i^(1/2) and the weight-averagemolecular weight Mi at each eluted volume obtained by the measurement inaccordance with GPC/MALLS described above by calculation in each rangeof the molecular weight in accordance with the following equation:G=Σwi·(<R ² >i ^(1/2) /<R ²>^(1/2) _(L))/Σwiwherein wi represents the concentration (the fraction by weight) at eacheluted volume. The calculation was conducted assuming that<R ²>^(1/2) _(L)=0.024×Mi ^(0.6)

It is necessary that the propylene composition of the present inventionhas an upturn from the inflection point (the strain-hardening) in thecurve showing the change in the viscosity under extension with time. Theinflection point means the inflection point convex to the downwarddirection. When the upturn in the change in the viscosity underextension with time is absent, the ability for forming cells in thefoaming process decreases and the resistance to draw down during agingof the sheet deteriorates. An example of the curve exhibiting the changein the viscosity under extension with time is shown in FIG. 1.

As for the “upturn from the inflection point in the curve showing thechange in the viscosity under extension”, it is defined that “the curveshowing the change in the viscosity under extension has an inflectionpoint” when the viscosity under extension measured at the same time is1.5 times or more as much as the value shown by the viscosity curve3η(t) obtained by using the relaxation spectrum, which is obtained fromthe dynamic viscoelasticity in accordance with the following equation:

3η(t) = ∫_(−∞)^(∞)H(τ)τ(1 − 𝕖^(−t/τ)) 𝕕ln  τIn the above equation, H(τ) represents the relaxation spectrum and τrepresents the relaxation time.

In polypropylene composition I of the present invention, the degradationparameter D is 0.7 or greater, preferably 0.8 or greater and morepreferably 0.9 or greater. When D is smaller than 0.7, degradation ofthe resin (scission of molecules) is marked and the reuse of thepolypropylene composition becomes impossible. The sample after mixingwhich is used for obtaining the degradation parameter is obtained byplacing 20 g of a sample into LABO PLASTOMILL, which is a compact typetwin-screw mixer produced by TOYO SEIKI Co., Ltd., followed by mixing ata set temperature of 190° C. and a rotation speed of 50 rpm for 5minutes. The degradation parameter is the value defined based on thestorage modulus G′ obtained by the measurement of the dynamicviscoelasticity before and after the mixing at the frequency of 0.01rad/s, in accordance with the following equation:D=G′ _(a) /G′ _(b)wherein G′a is the storage modulus after the mixing and G′b is thestorage modulus before the mixing. The degradation parameter is relatedto the number of branching. Therefore, the value can be adjusted by theamount of the polyene used in the polymerization.

Polypropylene composition I of the present invention can be produced,for example, in accordance with the process comprising:

-   -   in the first polymerization stage, polymerizing or        copolymerizing propylene alone or propylene and at least one        monomer selected from ethylene and α-olefins having 4 to 20        carbon atoms in the presence of a metallocene catalyst; and    -   in the second polymerization stage, copolymerizing the        homopolymer or the copolymer obtained in the first        polymerization stage with at least one monomer selected from        ethylene, propylene, α-olefins having 4 to 20 carbon atoms,        styrenes and cyclic olefins in the presence of a polyene having        at least two polymerizable carbon-carbon double bonds in one        molecule.

Examples of the α-olefin having 4 to 20 carbon atoms include the samecompounds as those described as the examples of the α-olefins having 4to 20 carbon atoms in processes I and II described above.

As the polyene used in the second polymerization stage, any polyene canbe used as long as the polyene has at least two polymerizablecarbon-carbon double bonds in one molecule. Examples of the polyeneinclude the same compounds as those described as the examples of thepolyene in processes I and II described above.

Polypropylene composition II of the present invention will be describedin the following.

In polypropylene composition II of the present invention, the branchingparameter a is in the range of:

-   -   0.35<a≦0.57        and preferably in the range of:    -   0.45<a≦0.52.

When the branching parameter a exceeds 0.57, the number of theintroduced branches decreases and the workability in moldingdeteriorates since the points of entanglement decrease. When thebranching parameter a is smaller than 0.35, the number of the introducedbranches increases and gels tend to be formed.

The branching parameter a is measured in accordance with the same methodas that described for polypropylene composition I.

In propylene composition II of the present invention, in general, thebranching index g is in the following ranges:

-   -   0.75≦g<1.0 (when the molecular weight measured in accordance        with the light scattering method is 2,000,000 to 10,000,000)    -   090≦g<1.0 (when the molecular weight measured in accordance with        the light scattering method is 500,000 to a value smaller than        2,000,000); and preferably in the following ranges:    -   0.75≦g<0.90 (when the molecular weight measured in accordance        with the light scattering method is 2,000,000 to 10,000,000)    -   092≦g<1.0 (when the molecular weight measured in accordance with        the light scattering method is 500,000 to a value smaller than        2,000,000) due to the same reason as that for polypropylene        composition I.

The branching index g is measured in accordance with the same method asthat described for polypropylene composition I.

In polypropylene composition II of the present invention, it isnecessary that the amount of the fraction having high molecular weightsof 1,000,000 or greater as measured in accordance with the lightscattering method be 10% by weight or less and preferably 3% by weightor less. By decreasing the amount of the fraction having high molecularweights of 1,000,000 or greater, the fluidity of the polypropylenecomposition is improved. When the amount of the fraction having highmolecular weights exceeds 10% by weight, the fluidity becomes poor andgels are formed in a great amount.

Polypropylene composition II of the present invention can be produced,for example, in accordance with the process comprising:

-   -   in the first polymerization stage, polymerizing or        copolymerizing propylene alone or propylene and at least one        monomer selected from ethylene and α-olefins having 4 to 20        carbon atoms in the presence of a metallocene catalyst; and    -   in the second polymerization stage, copolymerizing the        homopolymer or the copolymer obtained in the first        polymerization stage with at least one monomer selected from        ethylene, propylene, α-olefins having 4 to 20 carbon atoms,        styrenes and cyclic olefins in the presence of a polyene having        at least two polymerizable carbon-carbon double bonds in one        molecule.

Examples of the α-olefin having 4 to 20 carbon atoms include the samecompounds as those described as the examples of the α-olefins having 4to 20 carbon atoms in processes I and II described above.

As the polyene used in the second polymerization stage, any polyene canbe used as long as the polyene has at least two polymerizablecarbon-carbon double bonds in one molecule. Examples of the polyeneinclude the same compounds as those described as the examples of thepolyene in processes I and II described above.

Polypropylene compositions I and II of the present invention arecharacterized in that no gels are formed when the compositions areformed into molded articles. The formation of gels can be examined, forexample, by visual observation when a foamed sheet is formed. When afilm is formed, the amount of gel can be quantitatively measured by agel counter. The number of the gel with a diameter of at least 0.2 mm is10 or less, preferably 3 or less and more preferably 1 or less per 1,000cm² of the film.

To polypropylene compositions I and II of the present invention, variousadditives such as antioxidants, inorganic fillers, ultraviolet lightabsorbents and anti-weatherability agents may be contained, wherenecessary.

Polypropylene compositions I and II can be used for forming moldedarticles and sheets in accordance with a process such as the injectionmolding or the blow molding. Foamed molded articles can be produced byan extruder, in accordance with the chemical foaming or the physicalfoaming. Foamed sheets can be produced by a T-die or a round die. As thefoaming agent, at least one chemical foaming agent of the heatdecomposition type selected from azodicarbonamide, oxybisbenzenesulfonylhydrazide, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide,diazoaminobenzene and azobisisobutyronitrile can be used. The amount ofthe foaming agent can be suitably selected in accordance with theexpansion ratio of the foamed sheet.

The present invention also provides molded articles such as foamedmolded articles, sheets and other molded articles obtained by usingpolypropylene compositions I and II of the present invention describedabove.

A thermoplastic resin composition obtained by mixing a thermoplasticresin to at least one composition selected from the polyolefin-basedresin compositions obtained in accordance with processes I, II and IIIand polypropylene compositions I and II which are described above willbe described in the following.

The process for producing the thermoplastic resin composition obtainedby mixing a thermoplastic resin to at least one composition selectedfrom the polyolefin-based resin compositions obtained in accordance withprocesses I, II and III and polypropylene compositions I and II is notparticularly limited and the thermoplastic resin composition can beproduced in accordance with a conventional process.

Examples of the process include the melt mixing processes using mixersand extruders, examples of which include mixing processes using a mixingapparatus such as a single screw extruder, a twin screw extruder, a twinscrew mixer, a Banbury mixer and rolls. The composition is, in general,formed into pellets.

Alternatively, the constituting components of the thermoplasticcomposition may be dissolved into a solvent and the composition may berecovered by removing the solvent or by adding the solution into a poorsolvent of the polymer.

Examples of the thermoplastic resin which is used for the thermoplasticresin composition (this composition will be referred to as the abovethermoplastic resin composition, hereinafter) comprising thethermoplastic resin and a composition (this composition will be referredto as the above composition, hereinafter) selected from thepolyolefin-based resin compositions produced in accordance withprocesses I, II and III of the present invention described above andpolypropylene compositions I and II described above includepolyolefin-based thermoplastic resins, copolymers of olefins and vinylmonomers, modified olefin copolymers, condensation-based macromolecularcompounds and polymers obtained by addition polymerization. Examples ofthe polyolefin-based thermoplastic resin include homopolymers andcopolymers such as polyethylene, polypropylene, polystyrene, polybutene,ethyl/α-olefin copolymers, block polypropylene and low-densitypolyethylene produced in accordance with the high-pressure process.

Examples of the thermoplastic resin include copolymers of olefins andvinyl monomers, modified olefin copolymers, condensation-basedmacromolecular compounds and polymers obtained by polyadditionpolymerization. Examples of the copolymer of an olefin and a vinylmonomer which is a polymer obtained by addition polymerization includeethylene/vinyl acetate copolymers, ethylene/acrylic acid copolymers,ethylene/ethyl acrylate copolymers, ethylene/methyl methacrylatecopolymers, ionomers which are obtained by substituting metal ions incopolymers of ethylene and vinyl monomers containing carboxylic acid(for example, a substance obtained by neutralizing an ethylene/acrylicacid copolymer with sodium ion) and ethylene/vinyl alcohol copolymers.

Examples of the modified olefin copolymer include polypropylene modifiedwith maleic anhydride and polyethylene modified with maleic anhydride.

Examples of the condensation-based macromolecular compound includepolycarbonates, polyacetals, polyamides such as nylon 6 and nylon 6,6,polyesters such as polyethylene terephthalate and polybutyleneterephthalate, polyphenylene oxides, polysulfones, polyether sulfones,polyphenylene sulfides, polyimides and phenol resins.

Examples of the polymers obtained by addition polymerization (polymersobtained from polar vinyl monomers and diene-based monomers) includehomopolymers such as polymethyl methacrylate, polystyrene,polyacrylonitrile, polyvinyl chloride, polybutadiene, polyisoprene andpolyvinyl alcohol; acrylonitrile/butadiene/styrene copolymers;hydrogenated polymers such as SEBS; acrylonitrile/styrene copolymers;high impact polystyrene (modified with rubber); petroleum resins; andthermoplastic rubbers.

The relative amounts of the above composition and the thermoplasticresin can be decided in accordance with the object. In general, thethermoplastic resin is used in an amount in the range of 0.01 to 100parts by weight per 1 part by weight of the above composition.

As the thermoplastic resin, polyolefin-based thermoplastic resins arepreferable.

Examples of the additive include antioxidants, hydrochloric acidadsorbents, light stabilizers, lubricants, nucleating agents, inorganicfillers, stabilizers and ultraviolet light absorbents.

As the antioxidant, phenol-based antioxidants, sulfur-based antioxidantsand phosphorus-based antioxidants can be used. It is preferable that theantioxidants, the hydrochloric acid adsorbents, the light stabilizers,the lubricants, the stabilizers and the ultraviolet light absorbentsamong the above additives are added into the above resin composition orthe above thermoplastic resin composition in amount in the range of0.0001 to 10% by mass.

The amount of the nucleating agent added into the composition is in therange of 0.001 to 10% by mass, preferably in the range of 0.01 to 5% bymass and more preferably in the range of 0.1 to 3% by mass. The amountof the inorganic filler added into the composition is in the range of0.1 to 60% by mass, preferably in the range of 0.3 to 50% by mass andmore preferably in the range of 1 to 40% by mass.

Examples of the phenol-based antioxidant include phenols such as2,6-di-t-butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl)thioglycolate, stearyl β-(4-hydroxy-3,5-di-t-butylphenol)propionate,distearyl 3,5-di-t-butyl-4-hydroxybenzyl phosphonate,2,4,6-tris(3′,5′-t-butyl-4′-hydroxybenzylthio)-1,3,5-triazine, distearyl(4-hydroxy-3-methyl-5-t-butylbenzyl)malonate,2,2′-methylenebis(4-methyl-6-t-butyl-phenol),4,4′-methylenebis(2,6-di-t-butylphenol),2,2′-methylenebis[6-(1-methylcyclohexyl)-p-cresol],bis[3,5-bis(4-hydroxy-3-t-butylphenyl)-butyric acid] glycol ester,4,4′-butylidenebis(6-t-butyl-m-cresol),1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,bis[2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butyl)benzylisocyanurate,1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,tetrakis-[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,2-octylthio-4,6-di(4-hydroxy-3,5-di-t-butyl)phenoxy-1,3,5-triazine and4,4′-thiobis(6-t-butyl-m-cresol); and oligoesters of carbonic acid withpolyhydric phenols such as oligoesters (for example, a degree ofpolymerization of 2 to 10) of carbonic acid with4,4′-butylidenebis(2-t-butyl-5-methylphenol).

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristylthiodipropionate and distearyl thiodipropionate; and esters ofalkylthiopropionic acids such as butylthiopropionic acid,octylthio-propionic acid, laurylthiopropionic acid andstearylthiopropionic acid with polyhydric alcohols such aspentaerythritol tetralaurylthiopropionate. Examples of the polyhydricalcohol include glycerol, trimethylolethane, trimethylolpropane,pentaerythritol and trishydroxyethyl isocyanurate.

Examples of the phosphorus-based antioxidant include trioctyl phosphite,trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite,tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite,tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)1,1,3-tris(2-methyl-5-t-butyl-4-hydroxyphenyl)butane diphosphite,tetra(mixed alkyl having 12 to 15 carbon atoms)4,4-isopropylidenediphenyl diphosphite, tetra(tridecyl)4,4-butylidenebis(3-methyl-6-t-butylphenol) diphosphite,tris(3,5-di-t-butyl-4-hydroxyphenyl) phosphite, tris(mixed mono- anddi-nonylphenyl) phosphite, hydrogenated 4,4′-isopropylidenediphenolpolyphosphite, bis(octylphenyl)bis[4,4′-butylidenebis(3-methyl-6-t-butylphenol)] 1,6-hexanendioldiphosphite, phenyl 4,4′-isopropylidenediphenol pentaerythritoldiphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,tris[4,4′-isopropylidenebis(2-t-butylphenol)] phosphite, phenyldiisodecyl phosphite, di(nonylphenyl) pentaerythritol diphosphite,tris(1,3-distearoyloxyisopropyl) phosphite,4,4′-isopropylidene-bis(2-t-butylphenol) di(nonylphenyl) phosphite,9,10-dihydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide andtetrakis(2,4-di-t-butyl-phenyl)-4,4′-biphenylene diphosphonite.

Examples of the hydrochloric acid absorbent include calcium stearate,Mg₆Al₂(OH)₁₆CO₃.4H₂O, Mg₆Al₂(OH)₂₀CO₃.5H₂O, Mg₆Al₂(OH)₁₄CO₃.4H₂O,Mg₁₀Al₂(OH)₂₂(Ca3)₂.4H₂O, Mg₆Al₂(OH)₁₆HPO₄.4H₂O, Ca₆Al₂(OH)₁₆CO₃.4H₂O,Zn₆Al₂(OH)₁₆CO₃.4H₂), Zn₆Al₂(OH)₁₆SO₄.4H₂O, Mg₆Al₂(OH)₁₆SO₃.4H₂O andMg₆Al₂(OH)₁₂CO₃.3H₂O.

Examples of the light stabilizer include hydroxybenzophenones such as2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone,2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone;benzotriazoles such as2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-t-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methylphenyl)benzotriazole and2-(2′-hydroxy-3′,5′-di-t-amylphenyl)benzotriazole; phenyl salicylate;p-t-butylphenyl salicylate; benzoates such as 2,4-di-t-butylphenyl3′,5′-di-t-butyl-4-hydroxybenzoate and hexadecyl3′,5′-di-t-butyl-4-hydroxybenzoate; nickel compounds such as Ni salt of2,2′-thiobis(4-t-octylphenol), Ni salt of[2,2′-thiobis(4-t-octylphenolato)-n-butylamine and Ni salt of(3,5-di-t-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester;substituted acrylonitrile such as methylα-cyano-β-methyl-β-(p-methoxyphenyl)acrylate; oxalic acid diamides suchas N′-2-ethylphenyl-N-ethoxy-5-t-butylphenyloxalic acid diamide andN-2-ethylphenyl-N′-2-ethoxyphenyloxalic acid diamide; and hindered aminecompounds such as bis(2,2,6,6-tetramethyl-4-piperidine) sebacate,poly[{6-(1,1,3,3-tetramethylbutyl)imino}-1,3,5-triazine-2,4-diyl{4-(2,2,6,6-tetramethylpiperidyl)imino}hexamethylene]and condensation products of2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol and dimethylsuccinate.

Examples of the lubricant include aliphatic hydrocarbons such asparaffin wax, polyethylene wax and polypropylene wax; higher fatty acidssuch as capric acid, lauric acid, myristic acid, palmitic acid,margarine acid, stearic acid, arachidic acid and behenic acid; metalsalts of higher fatty acids such as lithium salts, calcium salts, sodiumsalts, magnesium salts and potassium salts; aliphatic alcohols such aspalmityl alcohol, cetyl alcohol and stearyl alcohol; aliphatic amidessuch as caproic acid amide, caprylic acid amide, lauric acid amide,myristic acid amide, palmitic acid amide and stearic acid amide; estersof aliphatic acids and alcohols; and fluorine compounds such asfluoroalkylcarboxylic acids, metal salts of fluoroalkylcarboxylic acidsand metal salts of fluoroalkylsulfonic acids.

As the nucleating agent, aromatic ester salts of phosphoric acid,dibenzylidenesorbitol, metal salts of aromatic carboxylic acids andmetal salts of aliphatic carboxylic acids can be used. In the presentinvention, aromatic ester salts of phosphoric acid anddibenzylidenesorbitol are preferable.

Examples of the aromatic ester salts of phosphoric acid include sodium2,2′-methylenebis(4,6-di-t-butylphenyl) phosphate, sodium2,2′-ethylidenebis(4,6-di-t-butylphenyl) phosphate, lithium2,2′-methylenebis(4,6-di-t-butylphenyl) phosphate, lithium2,2′-ethylidenebis(4,6-di-t-butylphenyl) phosphate, sodium2,2′-ethylidenebis(4-i-propyl-6-t-butylphenyl) phosphate, lithium2,2′-methylenebis(4-methyl-6-t-butylphenyl) phosphate, lithium2,2′-methylenebis(4-ethyl-6-t-butylphenyl) phosphate, calciumbis[2,2′-thiobis(4-methyl-6-t-butylphenyl) phosphate], calciumbis[2,2′-thiobis(4-ethyl-6-t-butylphenyl) phosphate], calciumbis[2,2′-thiobis(4,6-di-t-butylphenyl) phosphate], magnesiumbis[2,2′-thiobis(4,6-di-t-butylphenyl) phosphate], magnesiumbis[2,2′-thiobis(4-t-octylphenyl) phosphate], sodium2,2′-butylidenebis(4,6-dimethylphenyl) phosphate, sodium2,2′-butylidenebis(4,6-di-t-butylphenyl) phosphate, sodium2,2′-t-octylmethylenebis(4,6-dimethylphenyl) phosphate, sodium2,2′-t-octylmethylenebis(4,6-di-t-butylphenyl) phosphate, calciumbis(2,2′-methylenebis(4,6-di-t-butylphenyl) phosphate), magnesiumbis[2,2′-methylenebis(4,6-di-t-butylphenyl) phosphate, bariumbis[2,2′-methylenebis(4,6-di-t-butylphenyl) phosphate], sodium2,2′-methylenebis(4-methyl-6-t-butylphenyl) phosphate, sodium2,2′-methylenebis(4-ethyl-6-t-butylphenyl) phosphate, sodium(4,4-dimethyl-5,6-di-t-butyl-2,2′-biphenyl) phosphate, calciumbis[(4,4-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl) phosphate], sodium2,2′-ethylidenebis(4-m-butyl-6-t-butylphenyl) phosphate, sodium2,2′-methylenebis(4,6-dimethylphenyl) phosphate, sodium2,2′-methylenebis(4,6-diethylphenyl) phosphate, potassium2,2′-ethylidenebis(4,6-di-t-butylphenyl) phosphate, calciumbis-2,2′-ethylidenebis(4,6-di-t-butylphenyl) phosphate], magnesiumbis[2,2′-ethylidenebis(4,6-di-t-butylphenyl) phosphate], bariumbis[2,2′-ethylidenebis(4,6-di-t-butylphenyl) phosphate], aluminumtris[2,2′-methylenebis(4,6-di-t-butylphenyl) phosphate], aluminumtris[2,2′-ethylidenebis(4,6-di-t-butylphenyl) phosphate, combinations ofthese compounds, sodium bis(4-t-butylphenyl) phosphate, sodiumbis(4-methylphenyl) phosphate, sodium bis(4-ethylphenyl) phosphate,sodium bis(4-i-propylphenyl) phosphate, sodium bis(4-t-octylphenyl)phosphate, potassium bis(4-t-butylphenyl) phosphate, calciumbis(4-t-butylphenyl) phosphate, magnesium bis(4-t-butylphenyl)phosphate, lithium bis(4-t-butylphenyl)phosphate, aluminumbis(4-t-butylphenyl) phosphate and combinations of these compounds.Among the above compounds, sodium2,2′-methylenebis(4,6-di-t-butylphenyl) phosphate and sodiumbis(4-t-butylphenyl) phosphate are preferable.

Examples of the dibenzylidenesorbitol include1,3,2,4-dibenzylidenesorbitol,1,3-benzylidene-2,4-p-methylbenzylidenesorbitol,1,3-benzylidene-2,4-p-ethylbenzylidenesorbitol,1,3-p-methylbenzylidene-2,4-benzylidenesorbitol,1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol,1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol,1,3-p-ethylbenzylidene-2,4-p-methylbenzylidenesorbitol,1,3,2,4-di(p-methylbenzylidene)sorbitol,1,3,2,4-di(p-ethylbenzylidene)sorbitol,1,3,2,4-di(p-n-propylbenzylidene)sorbitol,1,3,2,4-di(p-i-propylbenzylidene)sorbitol,1,3,2,4-di(p-n-butylbenzylidene)sorbitol,1,3,2,4-di(p-s-butylbenzylidene)sorbitol,1,3,2,4-di(p-t-butylbenzylidene)sorbitol,1,3,2,4-di(2′,4′-dimethylbenzylidene)sorbitol,1,3,2,4-di-(p-methoxybenzylidene)sorbitol,1,3,2,4-di(p-ethoxybenzylidene)sorbitol,1,3-benzylidene-2,4-p-chlorobenzylidenesorbitol,1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol,1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol,1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol,1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol,1,3,2,4-di(p-chlorobenzylidene) sorbitol and combinations of thesecompounds. Among the above compounds, 1,3,2,4-dibenzylidenesorbitol,1,3,2,4-di(p-methylbenzylidene)sorbitol,1,3,2,4-di(p-ethylbenzylidene)sorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol,1,3,2,4-di(p-chlorobenzylidene)sorbitol and combinations of thesecompounds are preferable.

Examples of the metal salts of aromatic carboxylic acids and the metalsalts of aliphatic carboxylic acids include aluminum salt of benzoicacid, aluminum salt of p-t-butylbenzoic acid, sodium adipate, sodiumthiophenecarboxylate, sodium pyrrolcarboxylate and polymers such aspolymethylpentene-1. Inorganic compounds such as talc can also be usedas the nucleating agent.

Examples of the inorganic filler include powder fillers, flake fillers,fiber fillers and balloon-shaped fillers. Examples of the powder fillerinclude natural silicic acid and silicates such as fine powder of talc,kaolinite, sintered clay, pyrophilite, sericite and wollastonite;carbonates such as precipitated calcium carbonate, heavy calciumcarbonate and magnesium carbonate; hydroxides such as aluminum hydroxideand magnesium hydroxide; oxides such as zinc oxide and magnesium oxide;and synthetic silicic acid and silicates such as hydrated calciumsilicate, hydrated aluminum silicate, hydrated silicic acid andanhydrous silicic acid. Examples of the flake filler include mica.Examples of the fiber fillers include whiskers of basic magnesiumsulfate, whiskers of calcium titanate, whiskers of aluminum borate,sepiolite, PMF (processed mineral fiber), xonotlite, potassium titanateand erestadite. Examples of the balloon-shaped filler include glassballoon and fly ash balloons.

Examples of the stabilizer include phenol-based antioxidants such as2,6-di-t-butyl-4-methylphenol,tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnate)]methane,metaoctadecyl 3-(4′-hydroxy-3,5-di-t-butylphenyl)propionate,2,2′-methylenebis(4-methyl-6-t-butylphenol),4,4′-butylidenebis(3-methyl-6-t-butylphenol),4,4′-thiobis(3-methyl-6-t-butylphenyl),2,2-thiobis(4-methyl-6-t-butylphenol),1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and1,3,5-tris(2-methyl-4-hydroxy-5-t-butylphenol)butane; sulfur-basedantioxidants such as dilauryl thiodipropionate and distearylthiodipropionate; and phosphorus-based stabilizers such as tridecylphosphite and trinonyl phosphite. Examples of the ultraviolet lightabsorbent include 2-hydroxy-4-octoxybenzophenone, 2-ethylhexyl2-cyano-3,3-diphenylacrylate and p-octylphenyl salicylate.

EXAMPLES

The present invention will be described more specifically with referenceto examples in the following. However, the present invention is notlimited to the examples. Polyolefin-based resin compositions wereevaluated in accordance with the following methods.

-   (1) MI (the melt index) was measured in accordance with the method    of Japanese Industrial Standard K 7210 at a temperature of 230° C.    under a load of 21.18 N. The temperature was set at 190° C. for the    measurement of some types of the resin.-   (2) The bulk density was measured in accordance with the method of    Japanese Industrial Standard K 6721.-   (3) The tension MS in melted condition was measured by using    CAPILLAROGRAPH 1B produced by TOYO SEIKI Co., Ltd. under the    following condition:

Capillary: with the diameter of 2.095 mm; and with the length of 8.0 mmDiameter of cylinder: 9.6 mm Rate of extrusion from cylinder: 10mm/minute Winding speed: 3.14 m/minute Temperature: 190° C. or 230° C.

-   (4) For the examination of the presence or the absence of the    fraction insoluble in decaline at 135° C., a polyolefin-based resin    composition was dissolved into decaline at 135° C. under stirring in    an amount such that the concentration of the polymer was 0.1 to 0.3    g/deciliter. The resultant mixture was stirred for 2 hours and then    left standing. The presence or the absence of insoluble fractions    was examined by the visual observation.-   (5) The meso pentad fraction [mmmm] was measured as follows: a    polymer was dissolved into a mixed solvent composed of    1,2,4-trichlorobenzene and deuterated benzene in relative amounts by    volume of 90:10; the signal of methyl group was measured by using a    ¹³C-NMR apparatus (LA-500; produced by NIPPON DENSHI Co., Ltd.) at    130° C. in accordance with the method of complete decoupling of    proton; and the meso pentad fraction was determined from the    obtained signal of methyl group. The meso pentad fraction [mmmm] in    the present invention means the isotactic fraction as the pentad    unit in the chain of the propylene molecule measured by ¹³C-NMR    spectrum i9l as proposed by A. Zambelli et al. [Macromolecules, 6,    925 (1973)]. The assignment of the peaks in the measurement of the    ¹³C-NMR spectrum was made in accordance with the assignment proposed    by A. Zambelli et al. [Macromolecules, 8, 687 (1975)].

Example 1 Preparation of a Polypropylene Composition

(1) Preparation of an Aluminum Oxy Compound

Using 1,000 milliliters of a toluene solution of methylaluminoxane (1.47moles/liter; produced by Albemarle Co., Ltd.; the content oftrimethylaluminum: 14.5% by weight), the solvent was removed under areduced pressure (about 20 mmHg) at 60° C. After the resultant productwas kept in this condition for 4 hours, the temperature was lowered tothe room temperature and a dried-up methylaluminoxane was obtained.

To the dried-up methylaluminoxane, dehydrated toluene was added todissolve methylaluminoxane and the volume of the solution was adjustedat the volume of the solution before the solvent was removed. The amountof trimethylaluminum in the methylaluminoxane was determined inaccordance with ¹H-NMR and found to be 3.6% by weight. The amount of theentire aluminum was measured in accordance with the fluorescence X-raymethod (the ICP method) and found to be 1.32 moles/liter. The abovemixture was left standing for 48 hours and insoluble fractions wereprecipitated.

The portion of the solution was filtered through a G5 glass filter andmethylaluminoxane soluble in toluene was obtained. The concentration ofmethylaluminoxane as measured in accordance with the fluorescence X-raymethod (the ICP method) was 1.06 moles/liter.

(2) Preparation of a Carrier and a Supported Methylaluminoxane

70 g of SiO₂ (P-10; available from Fuji Silysia Co., Ltd.) was dried at140° C. for 15 hours under a nitrogen stream of a very small flow rate.The dried SiO₂ in an amount of 22.0 g was weighed and added into 200milliliters of dehydrated toluene. Under the atmosphere of nitrogen,after the temperature was kept at the constant value of 0° C. understirring, 200 milliliters of the toluene solution of methylaluminoxaneprepared in the foregoing term (1) was added dropwise over 60 minutes.When the dropwise addition was completed, the temperature was raised tothe room temperature and the reaction was allowed to proceed for 30minutes in this condition. The reaction was further allowed to proceedat 70° C. for 3 hours. After the reaction was completed, the reactionmixture was kept at 60° C. The solid component was washed twice with 200milliliters of dehydrated toluene and twice with 200 milliliters ofdehydrated heptane and dried at 50° C. under a reduced pressure and 32.8g of methylaluminoxane supported on SiO₂ was obtained. The obtainedsupporeted methylaluminoxane was added into dehydrated heptane and keptas a slurry.

(3) Preparation of a Supported Metallocene Catalyst

After a Schlenk tube with a volume of 50 milliliters was dried andpurged with nitrogen, 10 milliliters of dried heptane and 2 millimolesas aluminum atom conversion of the methylaluminoxane supported on SiO₂prepared in the foregoing term (2) were placed into the tube and thestirring was started. To the stirred mixture, 1 milliliter of a toluenesolution containing rac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ in an amount suchthat the amount of zirconium atom was 2 micromoles was slowly added andthe reaction was allowed to proceed for 10 minutes.

(4) Preparation of a Polypropylene Composition

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the supported catalyst prepared in theforegoing term (3) was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa for 30 minutes for activation of thecatalyst, the unreacted propylene was removed by releasing the pressureand blowing with nitrogen. Then, 0.02 MPa of hydrogen was introduced.The temperature was set at 70° C. and the polymerization was started byintroducing propylene at a partial pressure of 0.7 MPa. Polypropylenewas produced for 60 minutes while the temperature was controlled. Afterthe reaction was completed, the reaction mixture was lowered to the roomtemperature and the pressure was released. The reactor was sufficientlyblown with dry nitrogen and a portion of the reaction mixture was takenas a sample.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.2 millimole of1,9-decadiene (1.6×10⁻⁶ moles per 1 g of the polymer obtained in thefirst polymerization stage) was added. While the temperature wascontrolled at 40° C., propylene was introduced at a partial pressure of0.7 MPa and the polymerization was conducted for 30 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 152 g. The results of the measurements of the obtainedpolypropylene composition are shown in Table 3.

TABLE 3 Fraction Amount in in Fraction second second MI Bulk Meltinsoluble stage^(#) stage^(##) (g/10 density tension in (%) (g) min)(g/ml) (g) decaline Mw/Mn [η]₂/[η]₁ Example 1 16.8 25.6 0.87 0.45 16.8none 3.5 1.11 ^(#)The fraction of the polymer obtained in the secondpolymerization stage. ^(##)The amount of the polymer obtained in thesecond polymerization stage.

Examples 2 to 6 Various Values of Parameters in the Multi-stagePolymerization

Using the catalyst shown in Example 1 (3), polypropylene compositionswere prepared under various conditions shown in Table 4. The results ofthe measurements of the obtained polypropylene compositions are shown inTable 5.

TABLE 4 Condition of the first polymerization stage pressure hydro- oftem- SiO₂/MAO Zr gen propylene perature time (mmol-Al) (μmol) (ml) (MPa)(° C.) (min) Example 2 2.0 2 30 0.65 60 90 Example 3 2.0 2 30 0.65 60 90Example 4 2.0 2 30 0.65 60 90 Example 5 2.0 5 *0.02 0.65 60 90 Example 62.0 2 30 0.65 60 90 *The unit: MPa Condition of the secondpolymerization stage pressure of 1,9-decadiene propylene temperaturetime (mmol) * (MPa) (° C.) (min) Example 2 0.1 0.7 × 10⁻⁶ 0.65 40 60Example 3 0.2 1.2 × 10⁻⁶ 0.65 40 60 Example 4 0.3 2.0 × 10⁻⁶ 0.65 40 60Example 5 0.5 3.2 × 10⁻⁶ 0.70 60 60 Example 6 0.2 1.6 × 10⁻⁶ 0.65 30 60*Amount by mole per 1 g of the polymer obtained in the firstpolymerization stage.

TABLE 5 Fraction Amount in in Fraction Amount second second MI Bulk Meltinsoluble obtained stage^(#) stage^(##) (g/10 density tension in Mw/[η]₂/ Example (g) (%) (g) min) (g/ml) (g) decaline Mn [η]₁ 2 152 11.116.9 0.51 0.45 21.0 none 3.5 1.55 3 191 14.5 27.7 0.39 0.45 19.5 none3.5 1.96 4 174 12.4 21.6 0.47 0.44 18.0 none 3.2 1.92 5 190 19.0 36.19.04 0.45 6.5 none 8.4 1.50 6 138 10.7 14.8 0.32 0.45 18.5 none 3.4 2.00^(#)The fraction of the polymer obtained in the second polymerizationstage. ^(##)The amount of the polymer obtained in the secondpolymerization stage.

Examples 7 to 16 Various Polyenes

Polypropylene compositions were prepared in accordance with the sameprocedures as those conducted in Example 1 (4) except that polyenesshown in Table 6 were used in place of the polyene used in Example 1(4). The results of the measurements of the obtained polypropylenecompositions are shown in Table 6.

TABLE 6 Fraction Amount Amount in in polyene ob- second second Ex-amount tained stage^(#) stage^(##) ample compound (mmol) * (g) (%) (g) 7 divinyl- 0.2 1.6 × 10⁻⁶ 140 10.5 14.7 benzene  8 1,5-hexa- 0.2 2.0 ×10⁻⁶ 112 8.5 9.52 diene  9 1,6-hepta- 0.2 1.7 × 10⁻⁶ 133 9.5 12.6 diene10 1,7-octa- 0.2 1.7 × 10⁻⁶ 125 5.0 6.25 diene 11 p-3-butenyl- 0.2 1.7 ×10⁻⁶ 135 12.5 16.9 styrene 12 p-5-pro- 0.2 1.7 × 10⁻⁶ 130 11.5 15.0penylstyrene 13 norborna- 0.2 1.6 × 10⁻⁶ 141 12.5 17.6 diene 14 5-(3-0.2 1.8 × 10⁻⁶ 122 7.5 9.15 butenyl)bi- cyclo- [2.2.1]hept- 2-ene 155-vinyl- 2.0 1.9 × 10⁻⁵ 118 10.5 12.4 nobornene 16 dicyclo- 2.0 1.4 ×10⁻⁵ 157 8.5 13.3 pentadiene ^(#)The fraction of the polymer obtained inthe second polymerization stage. ^(##)The amount of the polymer obtainedin the second polymerization stage. *Amount by mole per 1 g of thepolymer obtained in the first polymerization stage. Fraction Bulk Meltinsoluble MI density tension* in [η]₂/ Example (g/10 min) (g/ml) (g)decaline Mw/Mn [η]₁  7 1.2 0.44 15.6 none 3.2 1.5  8 0.8 0.44 18.5 none3.1 1.6  9 0.8 0.45 17.6 none 3.1 1.9 10 1.3 0.44 14.5 none 2.8 2.2 112.0 0.42 11.0 none 3.2 2.1 12 1.0 0.45 15.3 none 3.6 1.6 13 1.1 0.4415.0 none 3.7 1.6 14 0.7 0.45 19.5 none 4.0 1.9 15 3.7 0.44 5.6 none 2.92.1 16 3.2 0.42 5.0 none 2.9 2.0 *Tension in melted condition wasmeasured at 230° C.

Comparative Example 1

A polypropylene composition was prepared in accordance with the sameprocedures as those conducted in Example 1 except that 1,9-decadiene wasnot used. As the result, 143 g of polypropylene was obtained. Theresults of the measurements of the obtained polypropylene compositionare shown in Table 7.

Comparative Example 2

A polypropylene composition was prepared in accordance with a singlestage process without conducting the second polymerization stage and1,9-decadiene used in Example 1 (4) was used in the preparation ofpolypropylene in the first polymerization stage. As the result, 123 g ofpolypropylene was obtained. The results of the measurements of theobtained polypropylene composition are shown in Table 7.

TABLE 7 Fraction Amount in in Tension* Fraction Amount second second MIBulk in melted insoluble Comparative obtained stage^(#) stage^(##) (g/10density condition in Mw/ [η]₂/ Example (g) (%) (g) min) (g/ml) (g)decaline Mn [η]₁ 1 143 16.2 23.1 1.3 0.43 2.5 none 3.5 1.15 2 123 0 00.02 0.38 ** found 2.5 — ^(#)The fraction of the polymer obtained in thesecond polymerization stage. ^(##)The amount of the polymer obtained inthe second polymerization stage. *Tension in melted condition wasmeasured at 230° C. **Infusible components were formed and themeasurement was impossible.

Examples 17 to 20 Preparation of Polypropylene Compositions usingVarious Complexes

(1) Supported Catalyst Components were Prepared in Accordance with thesame Procedures as those Conducted in Example 1 (3) except thatMetallocene Compounds shown in Table 8 were used in Place ofrac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ used in Example 1 (3).

(2) Condition of Preparation of Polypropylene Compositions

The conditions used in Example 1 (4) was changed so as to use 400milliliters of dehydrated heptane as the solvent and 0.5 millimole oftriisobutylaluminum and polypropylene compositions were prepared.

As the catalyst, the supported catalyst was used in an amount such thatthe entire amount of zirconium atom was 2 micromoles. The preliminarypolymerization was conducted at a temperature of 25° C. under apropylene pressure of 0.3 MPa for 30 minutes. In Example 17, the firstpolymerization stage was conducted at a temperature of 60° C. under apropylene pressure of 0.8 MPa for 40 minutes and the secondpolymerization stage was conducted in the presence of 0.2 millimole of1,9-decadiene at a temperature of 30° C. under a propylene pressure of0.7 MPa for 60 minutes. The conditions in Examples 18 to 20 are as shownin Table 8. As the result, 125 g of polypropylene was obtained inExample 17. The results of the measurements of the obtainedpolypropylene compositions are shown in Table 9.

TABLE 8 Condition of the first polymerization stage Metallocene pressuretem- Ex- compound hydro- of pro- pera- am- SiO₂/MAO com- amount genpylene ture time ple (mmol-Al) pound (μmol) (ml) (MPa) (° C.) (min) 172.5 A 5 0 0.8 60 40 18 2.5 B 10 0 0.8 55 90 19 2.5 C 10 0 0.7 50 90 202.5 A 5 5 0.8 60 40 A: rac-SiMe₂[2-Me-4,5-Benzo-Ind]₂ZrCl₂ B:rac-SiMe₂[2-Me-Ind]₂ZrCl₂ C: rac-iPrCpFluZrCl₂ Condition of the secondpolymerization stage pressure of 1,9-decadiene propylene temperaturetime (mmol) * (MPa) (° C.) (min) Example 17 0.2 0.7 × 10⁻⁶ 0.7 30 60Example 18 0.2 1.3 × 10⁻⁶ 0.7 30 60 Example 19 0.2 2.5 × 10⁻⁶ 0.7 30 60Example 20 0.2 1.3 × 10⁻⁶ 0.7 40 30 *Amount by mole per 1 g of thepolymer obtained in the first polymerization stage.

TABLE 9 Fraction Amount in in Tension* Fraction Amount second second MIBulk in melted insoluble obtained stage^(#) stage^(##) (g/10 densitycondition in Mw/ [η]₂/ Example (g) (%) (g) min) (g/ml) (g) decaline Mn[η]₁ 17 125 8.5 10.6 3.5 0.43 10.5 none 2.9 1.5 18 172 9.0 15.5 10.50.45 4.5 none 2.9 1.8 19 91.5 12.5 11.5 21.5 0.42 3.5 none 3.5 1.6 20165 4.7 7.8 11.0 0.41 6.5 none 2.8 1.2 ^(#)The fraction of the polymerobtained in the second polymerization stage. ^(##)The amount of thepolymer obtained in the second polymerization stage. *Tension in meltedcondition was measured at 230° C.

Examples 21 to 24 Preparation of Polypropylene Compositions usingComposite Supported Catalysts

(1) Preparation of Supported Catalyst Components

Catalysts were prepared in accordance with the same procedures as thoseconducted in Example 1 (3) except that two types of metallocenecompounds were used. The two catalyst components were used afterdissolving into 2 milliliters of dehydrated toluene in advance. Theconditions of the preparation are shown in Table 10.

(2) Preparation of Polypropylene Compositions

Polypropylene compositions were prepared using a composite supportedcatalyst in accordance with the same procedures as those conducted inExample 1 (4) except that some of the conditions of the preparation werechanged. In the second polymerization stage, 0.2 millimole of1,9-decadiene was used. This amount corresponds to 1.7×10⁻⁶ moles(Example 21), 2.2×10⁻⁶ moles (Example 22), 4.6×10⁻⁶ moles (Example 23)and 1.0×10⁻⁶ moles (Example 24) based on 1 g of the polymer obtained inthe first polymerization stage. The results of the measurements of theobtained polypropylene compositions are shown in Table 11.

TABLE 10 Metallocene compound 1 SiO₂/MAO amount Example (mmol-Al)compound (μmol) 21 2.0 rac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ 2.5 22 2.0rac-(1,2′-ethylene)(2,1′-ethylene)- 2.5 bis(indenyl)zirconium dichloride23 2.0 rac-SiMe₂[2-Me-4,5- 2.5 Benzo-Ind]₂ZrCl₂ 24 2.0rac-SiMe₂[2-Me-4,5- 2.5 Benzo-Ind]₂ZrCl₂ Metallocene compound 2 amountExample compound (μmol) 21 rac-SiMe₂[2-Me-4-Ph-Ind]₂HfCl₂ 2.5 22rac-SiMe₂[2-Me-4-Ph-Ind]₂HfCl₂ 2.5 23rac-ethandiyl(1-(4,7-diisopropylindenyl))- 2.5(2-(4,7-diisopropylindenyl)hafnium dichloride 24rac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ 2.5

TABLE 11 Fraction Amount in in Tension* Fraction Amount second second MIBulk in melted insoluble obtained stage# stage## (g/10 density conditionin Mw/ [η]₂/ Example (g) (%) (g) min) (g/ml) (g) decaline Mn [η]₁ 21 1204.0 4.8 0.53 0.45 18.5 none 2.8 1.52 22 95 4.5 4.3 23.2 0.38 17.0 none2.9 2.33 23 45 3.2 1.4 7.50 0.38 16.5 none 2.9 1.85 24 185 4.7 8.7 6.300.44 17.5 none 3.0 1.80 #The fraction of the polymer obtained in thesecond polymerization stage. ##The amount of the polymer obtained in thesecond polymerization stage. *Tension in melted condition was measuredat 230° C.

Example 25 Preparation of a Low Regularity Isotactic PolypropyleneComposition

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred at the room temperature for 10 minutes. To the obtainedsolution, 1.0 millimole of methylaluminoxane [1.47 moles/liter,Albemarle Co., Ltd.; the content of trimethylaluminum: 14.5% by weight]was added and 1 milliliter of a toluene solution containing 0.2micromoles ofrac-(1,2′-ethylene)-(2,1′-ethylene)bis(3-methylindenyl)zirconiumdichloride was added as the metallocene catalyst. Hydrogen in an amountof 30 milliliters was further added. The temperature was set at 60° C.and the polymerization was started by introducing propylene at a partialpressure of 0.65 MPa. Polypropylene was prepared for 30 minutes whilethe temperature was controlled. After the prescribed reaction time hadpassed, the gas components such as unreacted propylene was completelyremoved by releasing the pressure and blowing with nitrogen while thetemperature was maintained. The temperature was controlled at 30° C. anda sample was taken out under this condition. It was found that theproduct was completely dissolved. Then, 0.6 millimole of 1,9-decadienewas added and the resultant mixture was stirred for 10 minutes.Propylene was introduced at a pressure of 0.7 MPa and the polymerizationwas conducted at 40° C. for 20 minutes. The reaction mixture was cooledto the room temperature and the pressure was released. The reactionsystem was a homogeneous solution. The reaction mixture was added into agreat amount of methanol and a low stereoregularity polypropylenecomposition was recovered. The amount of the recovered product was 95 g.The amount of the used diene was 1.05×10⁻⁵ moles per 1 g of the polymerobtained in the first polymerization stage.

The obtained polypropylene composition was analyzed in accordance with¹³C-NMR and it was found that the stereoregularity expressed by mmmm was58.2%. The melt index measured in accordance with the method of JapaneseIndustrial Standard K 7210 at a temperature of 230° C. under a load of21.18 N was 2.3 g/10 min. The tension in melted condition was 17.5 g. Noportions insoluble in decaline at 135° C. were found.

Example 26 Preparation of a Polyethylene Composition

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliter of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred at the room temperature for 10 minutes. To the obtainedsolution, a catalyst which was similar to the catalyst prepared inExample 1 (3) was added in an amount such that the amount of zirconiumatom was 2 micromoles. Hydrogen was introduced at a pressure of 0.01 MPaand the temperature was set at 60° C. The polymerization was started byintroducing ethylene at a partial pressure of 0.7 MPa. Polyethylene wasprepared for 60 minutes while the temperature was controlled. After theprescribed reaction time had passed, the reaction mixture was cooled tothe room temperature. The pressure was released and the reaction systemwas sufficiently blown with dry hydrogen. A sample was taken out.

To the above polymerization system containing polyethylene, 2milliliters of a heptane solution containing 0.2 millimole of1.9-decadiene (in an amount by mole of 4.0×10⁻⁶ moles per 1 g of thepolymer obtained in the first polymerization stage) was added. While thetemperature was controlled at 30° C., ethylene was introduced at apartial pressure of 0.7 MPa and the polymerization was conducted for 15minutes. After the polymerization was completed, the pressure wasreleased and polyethylene was recovered. The amount of the recoveredpolyethylene was 52 g. The results of the measurements of the obtainedpolyethylene composition are shown in Table 12.

Example 27 Preparation of an Ethylene/1-octene Copolymer

An ethylene/1-octene copolymer was prepared in accordance with the sameprocedures as those conducted in Example 26 except that 2 milliliters of1-octene was introduced before hydrogen was introduced. As the result,63 g of the copolymer was obtained. The amount of the used 1,9-decadienein an amount of 0.2 millimole corresponds to 3.3×10⁻⁶ moles per 1 g ofthe polymer obtained in the first polymerization stage. The results ofthe measurements are shown in Table 12.

TABLE 12 Fraction Amount in in Tension** Fraction second second MI Bulkin melted insoluble stage# stage## (g/10 density Density* condition inMw/ [η]₂/ Example (%) (g) min) (g/ml) (g/cm³) (g) decaline Mn [η]₁ 264.5 2.34 2.1 0.43 — 11.3 none 2.9 1.50 27 4.2 2.65 15 0.35 0.93 4.5 none3.5 1.71 #The fraction of the polymer obtained in the secondpolymerization stage. ##The amount of the polymer obtained in the secondpolymerization stage. *Density was measured at 23° C. using a densitygradient tube. **Tension in melted condition was measured at 190° C.

Examples 28 Preparation of a Syndiotactic Polystyrene Composition

(1) Preparation of a Catalyst

Into a vessel sufficiently dried and purged with nitrogen, toluene, 38millimole of triisobutylaluminum, 16.8 millimole of methylaluminoxaneavailable from by Albemarle Co., Ltd. and 0.15 millimole ofoctahydrofluorenyltitanium trimethoxide were placed and theconcentration of titanium was adjusted at 3 millimole/liter. Thecomponents were mixed together and stirred for 1 hour to prepare acatalyst.

(2) Preparation of Syndiotactic Polystyrene (SPS)

Into a reactor sufficiently dried and purged with nitrogen, 5 liters ofstyrene and triethylaluminum in an amount such that the ratio of theamounts by mole of styrene/triethylaluminum was 3500/1 were placed.After the mixture of styrene and triethylaluminum was heated at atemperature of 85° C., 21 milliliters of the catalyst prepared in theforegoing term (1) was added and the polymerization was started. After 1hour, 3 liters of toluene was added to remove the unreacted styrene.After the solid-liquid separation of the obtained product, SPS of thefirst polymerization stage was prepared. A portion of SPS of the firstpolymerization stage was taken as a sample and evaluated. The amount ofthe obtained product was 1,100 g and the weight-average molecular weightwas 153,000.

Then, a solution obtained by dissolving 2 millimole of divinylbenzeneinto 100 milliliters of toluene was added over 10 minutes and theresultant mixture was kept being stirred for 10 minutes.

The temperature of the polymerization was set at 40° C. A mixture ofstyrene and triethylaluminum having the ratio of the amounts by mole ofstyrene/triethylaluminum adjusted at 3500/1 in advance in an amount of 1liter was added and the second polymerization stage was started. After15 minutes, the polymerization was discontinued by adding methanol. Theobtained polymer was washed with methanol and dried at 200° C. for 2hours. The amount of the obtained product was 1,150 g and the producthad a weight-average molecular weight of 164,000. [η]₂/[η]₁ was 2.62.The amount of the used diene was 1.8×10⁻⁶ per 1 g of the polymerobtained in the first polymerization stage.

Example 29

A polypropylene/polyethylene composition was prepared in accordance withthe same procedures as those conducted in Example 1 (4) except thatethylene was used in place of propylene as the monomer in the secondpolymerization stage. The amount of the obtained composition was 120 gand the fraction of the polyethylene produced in the secondpolymerization stage was 12.5%. To evaluate the uniformity of theobtained composition, a pressed sheet (the thickness: about 100 μm) wasprepared at 220° C. and examined by the visual observation. As theresult, no gels were found and the uniformity was excellent.

Example 30

(1) Preparation of a Supported Catalyst

A catalyst component was prepared in accordance with the same proceduresas those conducted in Example 1 (3) except that 5 micromoles ofrac-iPrCpFluZrCl₂ was used in place of rac-SiMe₂[2-Me-4-Ph-Ind]₂-ZrCl₂.

(2) Preparation of a Composition of Polyethylene with anEthylene/Norbornene Copolymer

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the supported catalyst prepared in theforegoing term (1) was added. After the preliminary polymerization wasconducted at 25° C. under an ethylene pressure of 0.2 MPa for 30 minutesfor activation of the catalyst, the unreacted ethylene was removed byreleasing the pressure and blowing with nitrogen. Then, 0.02 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing ethylene at a partial pressureof 0.7 MPa. Polyethylene was produced for 210 minutes while thetemperature was controlled. After the prescribed reaction time hadpassed, the reaction mixture was cooled to the room temperature and thepressure was released. The reactor was sufficiently blown with drynitrogen and a portion of the reaction mixture was taken as a sample.

To the above polymerization system containing polyethylene, 2milliliters of a heptane solution containing 0.2 millimole of1,9-decadiene was added and 73 milliliters of norbornene was also added.While the temperature was controlled at 80° C., ethylene was introducedat a partial pressure of 0.7 MPa and the polymerization was conductedfor 90 minutes. After the polymerization was completed, the pressure wasreleased and a composition was recovered. The amount of the compositionwas 31 g. The amount of the used diene was 1.3×10⁻⁵ moles per 1 g of thepolymer obtained in the first polymerization stage.

(3) Evaluation of Uniformity

To evaluate the uniformity of the obtained composition, a pressed sheet(the thickness: about 100 μm) was prepared at 220° C. and examined byvisual observation. As the result, no gels were found and the uniformitywas excellent.

Example 32 Preparation of a Polypropylene Composition

Into a round-bottomed flask having an inner volume of 200 milliliters,equipped with a stirrer and purged with nitrogen, 10 g ofdiethoxymagnesium and 80 milliliters of toluene were placed and asuspension was prepared. To the prepared suspension, 20 milliliters ofTiCl₄ was added. After the temperature was raised to 90° C., 27milliliters of n-butyl phthalate was added. The temperature was furtherraised to 115° C. and the reaction was allowed to proceed for 2 hoursunder stirring. After the reaction was completed, the reaction productwas washed twice with 100 milliliters of toluene at 90° C. and 20milliliters of TiCl₄ and 80 milliliters of toluene were freshly added.The reaction was allowed to proceed at 115° C. for 2 hours understirring. After the reaction was completed, the reaction product waswashed 10 times with 200 milliliters of n-heptane at 40° C. The contentof titanium in the obtained solid catalyst component was measured andfound to be 2.61% by weight.

(2) Preparation of a Polypropylene Composition

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 5 minutes at the room temperature. To the stirredsolution, 0.033 millimole of dicyclopentyldimethoxysilane was added andthe resultant mixture was stirred for 2 minutes. Then, the solidcatalyst component containing titanium prepared in the foregoing term(1) in an amount such that the amount of titanium atom was 0.033millimole was added. Hydrogen was introduced at a pressure of 0.02 MPa·Gand the temperature of the content was raised to 80° C. To the resultantmixture, propylene was added for 60 minutes while the pressure ofpropylene was adjusted at 0.8 MPa·G and polypropylene of the firstpolymerization stage was prepared.

After the reaction was completed, the unreacted gas was removed byreleasing the pressure and completely removed by purging with nitrogen.A small amount of the polymer was taken out and used as the sample forevaluating polypropylene obtained in the first polymerization stage. Asolution prepared by dissolving 4 mmol of divinylbenzene into 5 ml ofheptane was added into the autoclave over 30 seconds under stirring andthe stirring was continued for further 5 minutes.

Then, the temperature was set at 30° C. Propylene was introduced for 75minutes while the pressure was adjusted at 0.8 MPa·G and polypropyleneof the second polymerization stage was prepared. After the reaction wascompleted, the pressure was released. The content was added into 2liters of methanol and the formed polymer was recovered. The polymer wasseparated by filtration and dried under a stream of the air and in vacuoand 70.5 g of a polypropylene composition was obtained. The results ofthe measurements of the obtained polypropylene composition are shown inTable 13.

Example 33 Preparation of a Polypropylene Composition

(1) Preparation of a Catalyst Component

Into a three-necked flask having an inner volume of 500 milliliters,equipped with a stirrer and purged with nitrogen, 60 milliliters ofdehydrated octane and 16 g of diethoxymagnesium were placed and theresultant mixture was heated at 40° C. After 2.4 milliliters of silicontetrachloride was added to the heated mixture and the resultant mixturewas stirred for 20 minutes, 1.6 milliliters of dibutyl phthalate wasadded. The temperature of the resultant solution was raised to 80° C.and 77 milliliters of titanium tetrachloride was added. The operation ofbringing the components into contact with each other was conducted understirring at an inner temperature of 125° C. for 2 hours. Then, thestirring was stopped and the solid substances were precipitated. Thesupernatant liquid was separated and 100 milliliters of dehydratedoctane was added to the separated liquid. The temperature was raised to125° C. and kept at 125° C. for 1 minute under stirring. The stirringwas discontinued and the solid substances were precipitated. Then, thesupernatant liquid was separated. This operation of washing was repeated7 times. Then, 122 milliliters of titanium tetrachloride was added andthe second operation of bringing the components into contact with eachother was conducted at an inner temperature of 125° C. for 2 hours understirring. Thereafter, the washing with dehydrated octane at 125° C.described above was repeated 6 times and a solid catalyst component wasobtained.

(2) Preparation of a Polypropylene Composition

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated octane and 2.0millimole of triethylaluminum were placed and the resultant solution wasstirred for 5 minutes at the room temperature. To the stirred solution,0.1 millimole of dicyclopentyldimethoxysilane was added and theresultant mixture was stirred for 2 minutes. Then, the solid catalystcomponent containing titanium prepared in the foregoing term (1) in anamount such that the amount of titanium atom was 0.005 millimole wasadded. Hydrogen was introduced at a pressure of 0.05 MPa·G and thetemperature of the content was raised to 80° C. To the resultantmixture, propylene was added for 60 minutes while the pressure ofpropylene was adjusted at 0.8 MPa·G and polypropylene of the firstpolymerization stage was prepared.

After the reaction was completed, the unreacted gas was removed byreleasing the pressure and completely removed by purging with nitrogen.A small amount of the polymer was taken out and used as the sample forevaluating polypropylene obtained in the first polymerization stage. Asolution prepared by dissolving 4 millimole of divinylbenzene into 5milliliters of heptane was added into the autoclave over 30 secondsunder stirring and the stirring was continued for further 5 minutes.

Then, the temperature was set at 30° C. Propylene was introduced for 75minutes while the pressure was adjusted at 0.8 MPa·G and polypropyleneof the second polymerization stage was prepared. After the reaction wascompleted, the pressure was released. The content was added into 2liters of methanol and the formed polymer was recovered. The polymer wasseparated by filtration and dried in vacuo under a stream of the air and175 g of a polypropylene composition was obtained. The results of themeasurements of the obtained polypropylene composition are shown inTable 13.

Example 34 Preparation of a Polypropylene Composition

(1) Preparation of a Catalyst Component

Into a three-necked flask having an inner volume of 500 milliliters,equipped with a stirrer and purged with nitrogen, 16 g ofdiethoxymagnesium (0.14 moles) was placed and 60 milliliters ofdehydrated octane was added. The resultant solution was heated at 40° C.After 2.4 milliliters (22.5 millimole) of silicon tetrachloride wasadded to the heated solution and the obtained solution was stirred for20 minutes, 12.7 millimole of di-n-butyl phthalate was added. Thetemperature of the resultant mixture was raised to 80° C. and 77milliliters (0.70 moles) of titanium tetrachloride was dripped through adropping funnel. The operation of supporting was conducted understirring at an inner temperature of 110° C. for 2 hours. Then, theobtained product was sufficiently washed with dehydrated heptane. Forthe second operation of supporting, 122 milliliters (1.12 moles) oftitanium tetrachloride was added and the resultant mixture was stirredfor 2 hours while the inner temperature was adjusted at 110° C. Theobtained product was sufficiently washed with dehydrated heptane and asolid product was obtained.

(2) Preparation of a Solid Catalyst Component (the Contact of the SolidProduct, an Organoaluminum and an Organosilane Component

Into a three-necked flask having an inner volume of 500 milliliters,equipped with a stirrer and purged with nitrogen, 10 g (3.3millimole-Ti) of the above solid product was placed and 60 millilitersof dehydrated heptane was added. After the resultant mixture was heatedat 40° C., 46.2 millimole of triethylaluminum and 82.5 millimole ofdicyclopentyldimethoxysilane were added. The obtained mixture wasstirred for 12 hours and the product was washed sufficiently withdehydrated heptane. The obtained solid component was used as the solidcatalyst component.

(3) Preparation of a Polypropylene Composition

In accordance with the same procedures as those conducted in Example 33(2) except that 400 milliliters of dehydrated heptane as the solvent,0.25 millimole of dicyclopentyldimethoxysilane, 0.1 MPa·G of hydrogenand the solid catalyst component containing titanium prepared in theforegoing term (2) in an amount such that the amount of titanium atomwas 0.005 millimole were used, 155 g of a polypropylene composition wasobtained. The results of the measurements of the obtained polypropylenecomposition are shown in Table 13.

TABLE 13 Fraction in Tension* Fraction Amount second MI* of meltedinsoluble obtained stage# [η]₂/ (g/10 mmmm condition in (g) (%) [η]₁min) (%) (g) decaline Example 32 70.5 7.5 2.5 8.4 99.0 1.1 none Example33 175 8.6 5.2 35 99.4 0.8 none Example 34 155 5.2 5.1 30 97.3 0.7 none#The fraction of the polymer obtained in the second polymerizationstage. *MI and the tension in melted condition were measured at 230° C.

Examples 35 to 39

Polypropylene compositions were prepared using 400 milliliters ofdehydrated heptane as the solvent, 10 millimole of triisobutylaluminum,0.033 millimole of dicyclopentyldimethoxysilane, 0.0033 millimole of thesolid catalyst prepared in Example 32 (1) and the polyenes shown inTable 14 under the conditions also shown in Table 14. The results of themeasurements of the obtained polypropylene compositions are shown inTable 15.

Comparative Example 3

A polypropylene composition was prepared in accordance with the sameprocedures as those conducted in Example 35 except that 1,9-decadienewas not used. The results of the measurements of the obtainedpolypropylene composition are shown in Table 15.

TABLE 14 Condition of the first polymerization stage pressure ofpressure of hydrogen propylene temperature time (MPa · G) (MPa · G) (°C.) (min) Example 35 0.5 0.8 80 60 Comparative 0.5 0.8 80 60 Example 3Example 36 0.2 0.8 80 60 Example 37 0.2 0.8 80 60 Example 38 0.2 0.8 8060 Example 39 0.2 0.8 80 60 Condition of the second polymerization stagepolyene pressure of tem- amount propylene perature time compound (mmol)(MPa · G) (° C.) (min) Example 35 1,9-decadiene 2.0 0.8 40 60Comparative — — 0.8 40 60 Example 3 Example 36 1.9-decadiene 4.0 0.8 40200  Example 37 1,7-octadiene 4.0 0.8 30 60 Example 38 p-3-butenyl- 4.00.8 40 60 styrene Example 39 p-5-propenyl- 4.0 0.8 40 60 styrene

TABLE 15 Fraction in Tension* Fraction Amount second MI* in meltedinsoluble obtained stage# [η]₂/ (g/10 mmmm condition in (g) (%) [η]₁min) (%) (g) decaline Example 35 74.6 5.9 3.3 16.2 98.8 0.7 noneComparative 72.0 5.8 3.3 15.8 98.9 0.25 none Example 3 Example 36 73.55.2 3.5 8.5 98.7 1.1 none Example 37 75.5 7.1 3.5 8.2 98.5 1.2 noneExample 38 85.5 4.6 3.2 4.2 98.2 2.3 none Example 39 82.2 3.9 3.6 3.899.0 2.2 none #The fraction of the polymer obtained in the secondpolymerization stage. *MI and the tension in melted condition weremeasured at 230° C.

Examples 40 to 43

Olefin-based polymers were prepared using 400 milliliters of dehydratedheptane as the solvent, 10 millimole of triisobutylaluminum, 0.033millimole of dicyclopentyldimethoxysilane, 0.0033 millimole of the solidcatalyst prepared in Example 32 (1) and the polyenes shown in Table 16under the conditions also shown in Table 16.Dicyclopentyldimethoxysilane was not used in Example 43. The results ofthe measurements of the obtained polypropylene composition are shown inTable 17.

TABLE 16 Condition of the first polymerization stage monomer pressure ofsupplied hydrogen pressure temperature time (MPa · G) compound (MPa · G)(° C.) (min) Example 40 0.2 propylene 0.8 80 60 ethylene 0.08 Example 410.2 propylene 0.8 80 60 ethylene 0.08 Example 42 0.2 propylene 0.8 80 60Example 43 2.5 ethylene 0.8 80 60 Condition of the second polymerizationstage monomer amount of supplied temper- 1,9-decadiene pressure aturetime (mmol) compound (MPa · G) (° C.) (min) Example 40 4.0 propylene 0.840 60 Example 41 4.0 ethylene 0.6 40 60 Example 42 4.0 ethylene 0.8 3020 Example 43 4.0 ethylene 0.8 30 20

TABLE 17 Fraction in Tension* Fraction Amount second MI* of meltedinsoluble obtained stage# [η]₂/ (g/10 mmmm condition in (g) (%) [η]₁min) (%) (g) decaline Example 40 79.5 6.6 3.3 5.5 — 1.5 none Example 4185.2 5.8 3.7 5.9 — 2.5 none Example 42 65.5 7.2 2.7 6.9 — 1.4 noneExample 43 112 2.1 4.1 2.6 — 3.1 none #The fraction of the polymerobtained in the second polymerization stage. *MI and the tension inmelted condition were measured at 230° C. in Examples 40 to 42 and 190°C. in Example 43.

Example 44 Preparation of a Polypropylene Composition

(1) Preparation of an Aluminum Oxy Compound

Using 1,000 milliliters of a toluene solution of methylaluminoxane (1.47moles/liter; available from Albemarle Co., Ltd.; the content oftrimethylaluminum: 14.5% by weight), the solvent was removed under areduced pressure (about 20 mmHg) at 60° C. After the resultant productwas kept in this condition for 4 hours, the temperature was lowered tothe room temperature and a dried-up methylaluminoxane was obtained.

To the dried-up methylaluminoxane, dehydrated toluene was added todissolve methylaluminoxane and the volume of the solution was adjustedat the volume of the solution before the solvent was removed. The amountof trimethylaluminum in the methylaluminoxane was determined inaccordance with ¹H-NMR and found to be 3.6% by weight. The amount of theentire aluminum was measured in accordance with the fluorescence X-raymethod (the ICP method) and found to be 1.32 moles/liter. The abovemixture was left standing for 48 hours and insoluble fractions wereprecipitated.

The portion of the solution was filtered through a G5 glass filter andmethylaluminoxane soluble in toluene was obtained. The concentration ofmethylaluminoxane as measured in accordance with the fluorescence X-raymethod (the ICP method) was 1.06 moles/liter.

(2) Preparation of a Carrier and a Supported Methylaluminoxane

70 g of SiO₂ (P-10; available from FUJI SILYSIA Co., Ltd.) was dried at140° C. for 15 hours under a nitrogen stream of a very small flow rate.The dried SiO₂ in an amount of 22.0 g was weighed and added into 200milliliters of dehydrated toluene. Under an atmosphere of nitrogen,after the temperature was kept at the constant value of 0° C. understirring, 200 milliliters of the toluene solution of methylaluminoxaneprepared in the foregoing term (1) was added dropwise over 60 minutes.When the dropwise addition was completed, the temperature was raised tothe room temperature and the reaction was allowed to proceed for 30minutes in this condition. The reaction was further allowed to proceedat 70° C. for 3 hours. After the reaction was completed, the reactionmixture was kept at 60° C. The solid component was washed twice with 200milliliters of dehydrated toluene and twice with 200 milliliters ofdehydrated heptane and dried at 50° C. under a reduced pressure and 32.8g of methylaluminoxane supported on SiO₂ was obtained. The obtainedmethylaluminoxane was added into dehydrated heptane and kept as slurry.

(3) Preparation of a Supported Metallocene Catalyst

After a Schlenk tube with a volume of 50 milliliters was dried andpurged with nitrogen, 10 milliliters of dried heptane and themethylaluminoxane supported on SiO₂ prepared in the foregoing term (2)in an amount such that the amount of aluminum atom was 2 millimole wereplaced into the tube and the stirring was started. To the stirredmixture, 1 milliliter of a toluene solution containingrac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ in an amount such that the amount ofzirconium atom was 2 micromoles and1,2-ethanediyl(1-(4,7-diisopropylindenyl))(2-(4,7-diisopropylindenyl)hafniumdichloride in an amount such that the amount of zirconium atom was 3.0micromoles was slowly added and the reaction was allowed to proceed for10 minutes.

(4) Preparation of a Polypropylene Composition

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant mixturewas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the supported catalyst prepared in theforegoing term (3) was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 0.02 MPa ofhydrogen was introduced. The temperature was set at 70° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.7 MPa (a gauge pressure). Polypropylene was produced for60 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.2 millimole of1,9-decadiene was added. While the temperature was controlled at 40° C.,propylene was introduced at a partial pressure of 0.7 MPa (a gaugepressure) and the polymerization was conducted for 30 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 141 g. The amount of the used diene was 1.7×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage.

(5) Preparation of Pellets

To the polypropylene composition obtained in the foregoing term (4), 750ppm of a phosphorus-based antioxidant P-EPQ (available from SANDOZCompany) and 1,500 ppm of a phenol-based antioxidant IRGANOX 1010(available from CIBA SPECIALTY CHEMICALS Company) were added andsufficiently mixed together. The resultant mixture was melted and mixedby a 20 mm single screw mixer extruder and pelletized. Using theprepared pellets, evaluations described in the following were conducted.The results are shown in Table 18.

-   (i) The branching parameter a and the branching index g were    measured in accordance with the methods described above.-   (ii) The viscosity under elongation was measured by using MELTEN    RHEOMETER produced by TOYO SEIKI Co., Ltd. using a sample having the    shape of a rod with a diameter of 3 mm and a length of 20 cm at a    set temperature of 180° C. The measurement was conducted at three    strain rates of 0.1, 0.2 and 1.0 s⁻¹ and the presence or the absence    of the upturn in the viscosity under elongation was examined. The    upturn (the strain-hardening) was present at all strain rates.-   (iii) The degradation parameter was measured in accordance with the    following method. A sample in an amount of 20 g was placed into a    small twin screw mixer LABOPLASTOMILL produced by TOYO SEIKI Co.,    Ltd. and mixed at a set temperature of 190° C. at a rotation speed    of 50 rpm for 5 minutes. The measurement was also made using an    apparatus for measuring viscoelasticity produced by RHEOMETRCS    Company (RMS-800) at a set temperature of 190° C. The degradation    parameter D was calculated from the storage modulus G′ at a    frequency of 0.01 rad/s in accordance with the following equation:    D=G′a/G′b    wherein G′a represents the storage modulus after the mixing and G′b    represents the storage modulus before the mixing. The obtained value    of the degradation parameter D was 0.94.

Example 45

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the same supported catalyst as thatprepared in Example 44 (3) was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 0.05 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.6 MPa (a gauge pressure). Polypropylene was produced for40 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.5 millimole of1,9-decadiene was added. While the temperature was controlled at 60° C.,propylene was introduced at a partial pressure of 0.6 MPa (a gaugepressure) and the polymerization was conducted for 30 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 135 g. The amount of the used diene was 4.6×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the sameprocedures as those conducted in Example 44. The results are shown inTable 18.

Example 46

A polypropylene composition was prepared in accordance with the sameprocedures as those conducted in Example 45 except that the pressure ofthe introduced hydrogen was change from 0.05 MPa (a gauge pressure) to0.025 MPa (a gauge pressure) and the temperature of the reaction waschanged from 60° C. to 30° C. The amount of the polypropylenecomposition was 155 g. The amount of the used diene was 1.1×10⁻⁵ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the sameprocedures as those conducted in Example 44. The results are shown inTable 18.

Example 47

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the same supported catalyst as thatprepared in Example 44 (3) was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 3 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.65 MPa (a gauge pressure). Polypropylene was produced for90 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.2 millimole of1,9-decadiene was added. While the temperature was controlled at 60° C.,propylene was introduced at a partial pressure of 0.65 MPa and thepolymerization was conducted for 90 minutes. After the polymerizationwas completed, the pressure was released and a polypropylene compositionwas recovered. The amount of the polypropylene composition was 162 g.The amount of the used diene was 1.5×10⁻⁶ moles per 1 g of the polymerobtained in the first polymerization stage. The physical properties wereevaluated in accordance with the same procedures as those conducted inExample 44. The results are shown in Table 18.

Example 48

A polypropylene composition was prepared in accordance with the sameprocedures as those conducted in Example 47 except that the amount ofthe used 1,9-decadiene was changed from 0.2 millimole to 0.1 millimoleand the polymerization time after adding 1,9-decadiene was changed from90 minutes to 60 minutes. The amount of the polypropylene compositionwas 137 g. The amount of the used diene was 0.8×10⁻⁶ moles per 1 g ofthe polymer obtained in the first polymerization stage. The physicalproperties were evaluated in accordance with the same procedures asthose conducted in Example 44. The results are shown in Table 18.

Example 49

A polypropylene composition was prepared in accordance with the sameprocedures as those conducted in Example 47 except that amount of theused 1,9-decadiene was changed from 0.2 millimole to 0.3 millimole andthe polymerization time after adding 1,9-decadiene was changed from 90minutes to 60 minutes. The amount of the polypropylene composition was149 g. The amount of the used diene was 2.5×10⁻⁶ moles per 1 g of thepolymer obtained in the first polymerization stage. The physicalproperties were evaluated in accordance with the same procedures asthose conducted in Example 44. The results are shown in Table 18.

Example 50

A polypropylene composition was prepared in accordance with the sameprocedures as those conducted in Example 47 except that thepolymerization time after adding 1,9-decadiene was changed from 90minutes to 180 minutes. The amount of the polypropylene composition was175 g. The amount of the used diene was 1.6×10⁻⁶ moles per 1 g of thepolymer obtained in the first polymerization stage. The physicalproperties were evaluated in accordance with the same procedures asthose conducted in Example 44. The results are shown in Table 18.

Comparative Example 4

A polypropylene E-105GM available from IDEMITSU PETROCHEMICAL Co., Ltd.in an amount of 200 g was placed into a bag made of polyethylene anddegassed. The degassed polypropylene was irradiated with electron beamsin an amount of 30 kGy using an electron accelerator. The pellets ofpolypropylene taken out of the bag was immediately placed into an ovenset at 140° C. and treated by heating for 10 minutes and pelletsirradiated with electron beams were obtained. The measurements and themolding were conducted in accordance with the same methods as those inExample 44. The results are shown in Table 18.

TABLE 18 Example 44 45 46 47 Branching parameter a 0.51 0.39 0.36 0.50Dependency of branching on molecular weight (branching index g)molecular weight: 2,000,000 to 0.87 0.76 0.77 0.86 10,000,000 molecularweight: 500,000 to smaller 0.98 0.97 0.94 0.97 than 2,000,000Degradation parameter D 0.94 0.96 0.95 0.98 Viscosity under elongation*sh sh sh sh Com- parative Example Example 48 49 50 4 Branching parametera 0.56 0.45 0.53 0.29 Dependency of branching on molecular weight(branching index g) molecular weight: 2,000,000 to 0.92 0.83 0.76 0.7210,000,000 molecular weight: 500,000 to smaller 0.99 0.98 0.90 0.89 than2,000,000 Degradation parameter D 0.98 0.96 0.95 0.68 Viscosity underelongation* sh sh sh sh *sh: Strain-hardening was found at each strainrate

Example 51 Preparation of a Polypropylene Composition

(1) Preparation of an Aluminum Oxy Compound

Using 1,000 milliliters of a toluene solution of methylaluminoxane (1.47moles/liter; available from Albemarle Co., Ltd.; the content oftrimethylaluminum: 14.5% by weight), the solvent was removed under areduced pressure (about 20 mmHg) at 60° C. After the resultant productwas kept in this condition for 4 hours, the volume of the solution wasadjusted at the volume of the solution before the solvent was removed.The amount of trimethylaluminum in the methylaluminoxane was determinedin accordance with ¹H-NMR and found to be 3.6% by weight. The amount ofthe entire aluminum was measured in accordance with the fluorescenceX-ray method (the ICP method) and found to be 1.32 moles/liter. Theabove mixture was left standing for 48 hours and insoluble fractionswere precipitated.

The portion of the solution was filtered through a G5 glass filter andmethylaluminoxane soluble in toluene was obtained. The concentration ofmethylaluminoxane as measured in accordance with the fluorescence X-raymethod (the ICP method) was 1.06 moles/liter.

(2) Preparation of a Carrier and a Supported Methylaluminoxane

70 g of SiO₂ (P-10; available from Fuji Silysia Co., Ltd.) was dried at140° C. for 15 hours under a nitrogen stream of a very small flow rate.The dried SiO₂ in an amount of 22.0 g was weighed and added into 200milliliters of dehydrated toluene. Under an atmosphere of nitrogen,after the temperature was kept at the constant value of 0° C. understirring, 200 milliliters of the toluene solution of methylaluminoxaneprepared in the foregoing term (1) was added dropwise over 60 minutes.When the dropwise addition was completed, the temperature was raised tothe room temperature and the reaction was allowed to proceed for 30minutes in this condition. The reaction was further allowed to proceedat 70° C. for 3 hours. After the reaction was completed, the reactionmixture was kept at 60° C. The solid component was washed twice with 200milliliters of dehydrated toluene and twice with 200 milliliters ofdehydrated heptane and dried at 50° C. under a reduced pressure and 32.8g of methylaluminoxane supported on SiO₂ was obtained. The obtainedmethylaluminoxane was added into dehydrated heptane and kept as slurry.The ratio of the amounts by weight of SiO₂/methylaluminoxane was 1/0.43.

(3) Preparation of a Supported Metallocene Catalyst

After a Schlenk tube with a volume of 50 milliliters was dried andpurged with nitrogen, 10 milliliters of dried heptane and themethylaluminoxane supported on SiO₂ prepared in the foregoing term (2)in an amount such that the amount of aluminum atom was 2 millimole wereplaced into the tube and the stirring was started. To the stirredmixture, 1 milliliter of a toluene solution containingrac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ in an amount such that the amount ofzirconium atom was 2 micromoles was slowly added and the reaction wasallowed to proceed for 10 minutes.

(4) Preparation of a Polypropylene Composition

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the supported catalyst prepared in theforegoing term (3) was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 0.02 MPa ofhydrogen was introduced. The temperature was set at 70° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.7 MPa (a gauge pressure). Polypropylene was produced for60 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.2 millimole of1,9-decadiene was added. While the temperature was controlled at 40° C.,propylene was introduced at a partial pressure of 0.7 MPa and thepolymerization was conducted for 30 minutes. After the polymerizationwas completed, the pressure was released and a polypropylene compositionwas recovered. The amount of the polypropylene composition was 152 g.The amount of the used diene was 1.5×10⁻⁶ moles per 1 g of the polymerobtained in the first polymerization stage.

(5) Preparation of Pellets

To the polypropylene composition obtained in the foregoing term (4), 750ppm of a phosphorus-based antioxidant P-EPQ (available from SANDOZCompany) and 1,500 ppm of a phenol-based antioxidant IRGANOX 1010(available from CIBA SPECIALTY CHEMICALS Company) were added andsufficiently mixed together. The resultant mixture was melted and mixedby a 20 mm single screw mixer extruder and pelletized. Using theprepared pellets, evaluations described in the following were conducted.The results are shown in Table 19. MI (the melt index) was 0.87 g/10minutes and no fractions insoluble in decaline at 135° C. werecontained.

-   (i) MI (the melt index) was measured in accordance with the method    of Japanese Industrial Standard K 7210 at a temperature of 230° C.    under a load of 21.18 N.-   (ii) The presence or the absence of the fraction insoluble in    decaline was examined by dissolving a polyolefin-based resin    composition at 135° C. under stirring in an amount such that the    concentration of the polymer was adjusted at 0.1 to 0.3 g/deciliter    and evaluated by visual observation after the mixture was stirred    for 2 hours and was then left standing.-   (iii) The branching parameter a and the branching index g were    measured in accordance with the methods described above.-   (iv) The amount of high molecular weight components was obtained by    calculating the fraction by weight of the components having    molecular weights of 1,000,000 or greater in the curve of the    molecular weight distribution obtained by the measurements in    accordance with GPC/MALLS.

The recovery of strain was measured by an apparatus for measuring creepPSR200 produced by RHEOMETRICS Company. Using two sample pieces havingthe shape of a disk having a diameter of 25 mm, the measurement wasconducted under the conditions of a distance between gaps of 1.2 mm, atemperature of 190° C. and a shearing stress of 500 Pa. The stress wasreleased when 100 seconds passed after the application of the load ofstress. When the recovery of strain at the time when 200 seconds havepassed after the release of the stress is represented by γ_(r) and theshearing strain at the time when 100 seconds have passed after theapplication of the load of stress is represented by γ, the value of(γ_(r)/γ)×100 is used as the recovery of strain.

(6) Expansion Molding

To 100 parts by weight of the polypropylene composition obtained in theforegoing term (4), 5 parts by weight of a foaming agent (EE205;available from EIWA KASEI KOGYO Co., Ltd.,) was added. The resultantmixture was extruded by a single screw extruder of the V30 type producedby TANABE PLASTIC KIKAI Co., Ltd. (the diameter of the screw: 30 mm;L/D=40) and a foamed molded article having the shape of a rod wasobtained. The conditions of the extrusion were as follows: thetemperature of C1 was 210° C.; the temperature of C2 was 220° C.; thetemperatures of C3 to C5 were 180° C.; the temperature of the die was180° C.; the rotation speed was 50 rpm; and the amount of extrusion was2.5 kg/hr.

The density of the foamed molded article obtained above was obtained bydividing the weight of the article by the volume obtained by dipping thearticle into water and the expansion ratio was obtained from theobtained density. The presence or the absence of gel was examined byvisual observation. The results are shown in Table 19.

Example 52

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of a supported catalyst ofrac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ which was the same as that prepared inExample 51 (3) described above and contained 5 micromoles of zirconiumatom was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 5 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.6 MPa (a gauge pressure). Polypropylene was produced for40 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.5 millimole of1,9-decadiene was added. While the temperature was controlled at 60° C.,propylene was introduced at a partial pressure of 0.6 MPa (a gaugepressure) and the polymerization was conducted for 30 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 180 g. The amount of the used diene was 3.3×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the same methodsas those conducted in Example 51. The results are shown in Table 19.

Example 53

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of a supported catalyst ofrac-SiMe₂[2-Me-4-Ph-Ind]₂ZrCl₂ which was the same as that prepared inExample 51 (3) described above and contained 5 micromoles of zirconiumatom was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 2.5 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.6 MPa (a gauge pressure). Polypropylene was produced for40 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.5 millimole of1,9-decadiene was added. While the temperature was controlled at 60° C.,propylene was introduced at a partial pressure of 0.6 MPa (a gaugepressure) and the polymerization was conducted for 30 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 162 g. The amount of the used diene was 3.0×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the same methodsas those conducted in Example 51. The results are shown in Table 19.

Example 54

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the same supported catalyst as thatprepared in Example 51 (3) described above was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 3 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.65 MPa (a gauge pressure). Polypropylene was produced for90 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.2 millimole of1,9-decadiene was added. While the temperature was controlled at 40° C.,propylene was introduced at a partial pressure of 0.65 MPa (a gaugepressure) and the polymerization was conducted for 90 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 148 g. The amount of the used diene was 1.8×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the same methodsas those conducted in Example 51. The results are shown in Table 19.

Example 55

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the same supported catalyst as thatprepared in Example 51 (3) described above was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 3 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.65 MPa (a gauge pressure). Polypropylene was produced for90 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.1 millimole of1,9-decadiene was added. While the temperature was controlled at 60° C.,propylene was introduced at a partial pressure of 0.65 MPa (a gaugepressure) and the polymerization was conducted for 60 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 164 g. The amount of the used diene was 0.8×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the same methodsas those conducted in Example 51. The results are shown in Table 19.

Example 56

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the same supported catalyst as thatprepared in Example 51 (3) described above was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 3 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.65 MPa (a gauge pressure). Polypropylene was produced for90 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen. A portion of the reaction product was taken as the sample.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.3 millimole of1,9-decadiene was added. While the temperature was controlled at 40° C.,propylene was introduced at a partial pressure of 0.65 MPa (a gaugepressure) and the polymerization was conducted for 60 minutes. After thepolymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 155 g. The amount of the used diene was 2.5×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the same methodsas those conducted in Example 51. The results are shown in Table 19.

Example 57

Into a pressure-resistant autoclave made of stainless steel and having avolume of 1.6 liters, 400 milliliters of dehydrated heptane and 0.5millimole of triisobutylaluminum were placed and the resultant solutionwas stirred for 10 minutes at the room temperature. To the stirredsolution, the entire amount of the same supported catalyst as thatprepared in Example 51 (3) described above was added.

After the preliminary polymerization was conducted at 25° C. under apropylene pressure of 0.3 MPa (a gauge pressure) for 30 minutes foractivation of the catalyst, the unreacted propylene was removed byreleasing the pressure and blowing with nitrogen. Then, 3 MPa ofhydrogen was introduced. The temperature was set at 60° C. and thepolymerization was started by introducing propylene at a partialpressure of 0.65 MPa (a gauge pressure). Polypropylene was produced for90 minutes while the temperature was controlled. After the reaction wascompleted, the reaction mixture was cooled to the room temperature andthe pressure was released. The reactor was sufficiently blown with drynitrogen.

To the above polymerization system containing polypropylene, 2milliliters of a heptane solution containing 0.2 millimole of1,9-decadiene was added. While the temperature was controlled at 40° C.,propylene was introduced at a partial pressure of 0.65 MPa (a gaugepressure) and the polymerization was conducted for 180 minutes. Afterthe polymerization was completed, the pressure was released and apolypropylene composition was recovered. The amount of the polypropylenecomposition was 151 g. The amount of the used diene was 1.8×10⁻⁶ molesper 1 g of the polymer obtained in the first polymerization stage. Thephysical properties were evaluated in accordance with the same methodsas those conducted in Example 51. The results are shown in Table 19.

Comparative Example 5

A polypropylene composition was prepared in accordance with a singlestage polymerization which was similar to the process in Example 51except that, in stage (4), 1,9-decadiene was used in the preparation ofpolypropylene in the first polymerization stage and the secondpolymerization stage was not conducted. As the result, 123 g of apolypropylene composition was obtained. The physical properties wereevaluated in accordance with the same methods as those conducted inExample 51. The results are shown in Table 19. MI (the melt index) was0.02 g/10 minutes and a fraction insoluble in decaline at 135° C. wasfound. The tension in melted condition could not be measured due to thepresence of infusible components. The molecular weight distributioncalculated from the weight-average molecular weight and thenumber-average molecular weight obtained in accordance with GPC was 2.5(the insoluble fractions were removed by a filter before the measurementof GPC).

TABLE 19 Example 51 52 53 54 MI (g/10 min) 0.87 0.60 1.0 0.58 Branchingparameter a 0.51 0.39 0.36 0.50 Dependency of branching on molecu- larweight (branching index g) molecular weight: 2,000,000 to 0.87 0.76 0.770.86 10,000,000 molecular weight: 500,000 to smaller 0.98 0.97 0.94 0.97than 2,000,000 Amount of high molecular weight 1.3 1.9 0.7 2.4 fraction(%) Shear strain γ (%) 125 120 35 105 Recovery of strain γr (%) 27 77 7343 Expansion ratio (times the original 2.6 2.5 2.5 2.2 volume) Gel* vnfvnf vnf vnf Comparative Example Example 55 56 57 5 MI (g/10 min) 0.510.47 0.75 0.02 Branching parameter a 0.56 0.45 0.53 0.29 Dependency ofbranching on molecular weight (branching index g) molecular weight:2,000,000 to 0.92 0.83 0.95 0.62 10,000,000 molecular weight: 500,000 to0.99 0.98 0.99 0.75 smaller than 2,000,000 Amount of high molecular 2.72.9 1.6 12.6 weight fraction (%) Shear strain γ (%) 103 48 135 98Recovery of strain γr (%) 40 45 28 15 Expansion ratio (times the 2.0 2.02.6 — original volume) Gel* vnf vnf vnf great amount *vnf: No gel wasvisually found.

Example 58

(1) Preparation of a Supported Metallocene Catalyst

After a Schlenk tube with a volume of 200 milliliters was dried andpurged with nitrogen, methylaluminoxane supported on SiO₂ which wasprepared in Example 51 (2) in an amount such that the amount of aluminumatom was 8 millimole was placed into the tube and the stirring wasstarted.

Into the above tube, 4 milliliters of a toluene solution containing 8micromoles of rac-SiMe₂[2-Me-4,5-BebzoInd]₂ZrCl₂[racemi-dimethylsilandiylbis-1-(2-methyl-4,5-benzoindenyl)zirconiumdichloride] was slowly added and the reaction was allowed to proceed at25° C. for 15 minutes.

(2) Preparation of a Polypropylene Composition

After a pressure-resistant autoclave made of stainless steel and havinga volume of 13 liters was sufficiently dried, 7 liters of heptanedehydrated with nitrogen and a heptane solution of triisobutylaluminumin an amount such that the amount of aluminum atom was 7 millimole wereplaced under the atmosphere of nitrogen and the resultant solution wasstirred at the room temperature for 20 minutes.

To the above solution, the entire amount of the catalyst componentprepared in the foregoing term (1) was added. For the preliminaryactivation of the catalyst, the pressure of propylene was raised to 0.3MPa (the gauge pressure) at 25° C. over 10 minutes and the preliminarypolymerization was conducted under the constant pressure for 30 minutes.

Thereafter, the unreacted propylene was removed by releasing thepressure and blowing with nitrogen. Hydrogen in an amount of 16milliliters was added and the temperature was raised to 60° C. over 10minutes. Then, propylene was introduced over 20 minutes and the pressurewas raised to 0.65 MPa. The introduction of propylene was continuedwhile the pressure and the temperature were kept constant and thepolymerization was conducted for 95 minutes.

The introduction of propylene was stopped and 50 milliliters of aheptane solution containing 4 milliliters of 1,7-octadiene was added.The polymerization temperature was lowered to 50° C. During thisoperation, the diene component was dispersed uniformly in the reactionsystem.

The introduction of propylene was resumed and the polymerization wasconducted for 65 minutes while the temperature was kept at 50° C. andthe pressure was kept at 0.6 MPa. After the polymerization wascompleted, 50 milliliters of ethanol was added and the reaction wasstopped.

The pressure was released and a polypropylene composition was recovered.The amount of the recovered composition was 2,830 g.

The amount of the used diene was 1.4×10⁻⁵ moles per 1 g of the polymerobtained in the first polymerization stage.

The above procedures of the polymerization were conducted for 7 batchesand a polypropylene composition in the total amount of 21.2 kg wasprepared. The prepared resin composition was pelletized in accordancewith the same procedures as those conducted in Example 44.

(3) Expansion Molding

The obtained pellets in an amount of 20 kg and 20 kg of a polypropyleneEX-500F available from IDEMITSU PETROCHEMICAL Co., Ltd. were blended aspellets and used for the expansion molding. For the molding, a moldingmachine TEM-41SS produced by Toshiba Machine Co., Ltd. was used. Themolding was conducted under the following conditions: the rotation speedof the screw was 100 rpm; the set temperatures for C1 to C3 were 210°C.; the set temperatures for C4 to the die was 170° C.; the amount ofcarbon dioxide was about 1,000 g/hr; and the drawing speed was 3.5m/min.

The expansion ratio of the obtained foamed sheet was 3.5 and noprotrusions of gel were found in the sheet.

Comparative Example 6

(1) Procedures Similar to those Conducted in Example 58 (2) wereConducted Except that the First Polymerization Stage was not Conductedand the Preliminary Activation of the Catalyst and the SecondPolymerization Stage were Conducted.

Specifically, in the procedures similar to those conducted in Example 58(2), after the preliminary activation was conducted in the same manner,the unreacted propylene was removed by releasing the pressure andblowing with nitrogen. Then, 16 milliliters of hydrogen was added and 50milliliters of a heptane solution containing 4 milliliters of1,7-octadiene was added. The temperature was raised to 50° C. spending10 minutes.

Then, propylene was introduced spending 20 minutes and the pressure wasraised to 0.6 MPa. The introduction of propylene was continued while thepressure and the temperature were kept constant. The polymerization wascontinued until the amount of the propylene/1,7-octadiene copolymerobtained by the polymerization reached about the same as the amount inExample 58 (2) while the flow rate of propylene was monitored.

After the polymerization was conducted for 2 hours, 50 milliliters ofethanol was added and the polymerization was stopped.

The pressure was released and the polypropylene composition wasrecovered. The amount of the composition was 2,900 g.

The amount of the used diene per the amount of the obtainedpolypropylene was about the same as that in Example 58 (2).

The above procedures were conducted for 7 batches and apropylene/1,7-octadiene copolymer in the total amount of 22.0 kg wasprepared. The prepared resin composition was pelletized in accordancewith the same procedures as those conducted in Example 44.

(2) Expansion Molding

The obtained pellets in an amount of 20 kg and 20 kg of a polypropyleneEX-500F available from IDEMITSU PETROCHEMICAL Co., Ltd. were blended aspellets and used for the expansion molding. The molding was conducted inaccordance with the same procedures as those conducted in Example 58.The expansion ratio of the obtained foamed sheet was 3.1. Manyprotrusions of gel were found in the sheet and it was difficult that thesheet was used as a product.

INDUSTRIAL APPLICABILITY

In accordance with the process for producing the polyolefin-based resincomposition of the present invention, the workability in molding of thepolyolefin is improved and the polyolefin-based resin composition whichhas physical properties controlled in wide ranges and can beadvantageously used in the fields where workability is required such asthe sheet molding, the extrusion expansion molding, the blow molding,the profile extrusion molding the inflation film molding can beefficiently produced.

The polypropylene composition of the present invention provides sheets,blow molded articles and foamed articles of polypropylene which exhibitexcellent melting elasticity, little degradation in recycling to enablereusing and excellent extrusion property, emit no smell causing noadverse effects on the taste of foods, have excellent secondaryworkability, contain no gel and are inexpensive.

1. A process for producing a polyolefin-based resin composition whichcomprises: in a first polymerization stage, polymerizing orcopolymerizing at least one monomer selected from the group consistingof ethylene, propylene, an α-olefin comprising 4 to 20 carbon atoms, astyrene and a cyclic olefin, in the presence of a catalyst comprising acombination of a catalyst component (A) comprising at least one compoundselected from compounds of transition metals of Group 4 of the PeriodicTable comprising a cyclopentadienyl skeleton structure and a promotercomponent (B), thereby obtaining a homopolymer or copolymer; and in asecond polymerization stage, copolymerizing the homopolymer or thecopolymer obtained in the first polymerization stage with at least onemonomer selected from the group consisting of propylene, an α-olefincomprising 4 to 20 carbon atoms, a styrene and a cyclic olefin, in apresence of a polyene having at least two polymerizable double bonds inone molecule, wherein the polyene is at least one compound selected fromthe group consisting of a polyene of a styrene-compound, astyrene/α-olefin polyene which comprises a residue group of styrene anda residue group of an α-olefin in the same molecule, a compound offormula (VI)

wherein n is 0, 1, or 2, a compound of formula (VII)

wherein n is 0, 1, or 2, and m is an integer of from 1 to 11, and acompound of formula (VIII)

wherein n is an integer of from 0 to 6; the polyene being used in anamount of 1.0×10⁻⁷ to 1.0×10⁻³ moles per 1 g of the homopolymer or thecopolymer obtained in the first polymerization stage, with the provisothat, in the second polymerization stage, the homopolymer or thecopolymer obtained in the first polymerization stage is not polymerizedwith ethylene, wherein the composition produced by the process satisfiesthe following requirements (a) to (c); (a) the intrinsic viscosity [η]₂of a polyolefin obtained in the second polymerization stage is greaterthan the intrinsic viscosity [η]₁ of a polyolefin obtained in the firstpolymerization stage, (b) a ratio [η]₂/[η]₁=1.05 to 10, and (c) acontent of the polyolefin obtained in the second polymerization stage inthe polyolefin-based resin composition is 0.00 1 to 80% by weight.
 2. Aprocess for producing a polyolefin-based resin composition whichcomprises: in a first polymerization stage, polymerizing orcopolymerizing at least one monomer selected from the group consistingof ethylene, propylene, an α-olefin comprising 4 to 20 carbon atoms, astyrene and a cyclic olefin in a presence of a catalyst comprising acatalyst component (A) comprising at least one compound selected fromcompounds of transition metals of Group 4 of the Periodic Table having acyclopentadienyl skeleton structure and a promoter component (B); and ina second polymerization stage, copolymerizing the homopolymer or thecopolymer obtained in the first polymerization stage with at least onemonomer selected from the group consisting of, an α-olefin comprising 4to 20 carbon atoms, a styrene and a cyclic olefin in a presence of apolyene having at least two polymerizable carbon-carbon double bonds inone molecule, wherein the polyene is at least one compound selected froma polyene of a styrene-compound, a styrene/α-olefin polyene whichcomprises a residue group of styrene and a residue group of an α-olefinin the same molecule, a compound of formula (VI)

wherein n is, 0, 1, or 2, a compound of formula (VII)

wherein n is 0, 1, or 2, and m is an integer of from 1 to 11, and acompound of formula (VIII)

wherein n is an integer of from 0 to 6 and with the proviso that, in thesecond polymerization stage, the homopolymer or the copolymer obtainedin the first polymerization stage is not polymerized with ethylene,wherein the composition produced by the process satisfies the followingrequirements (a) to (c); (a) the intrinsic viscosity [η]2 of apolyolefin obtained in the second polymerization stage is greater thanthe intrinsic viscosity [η]1 of a polyolefin obtained in the firstpolymerization stage, (b) a ratio [η]2/[η]1=1.05 to 10, and (c) acontent of the polyolefin obtained in the second polymerization stage inthe polyolefin-based resin composition is 0.001 to 80% by weight.
 3. Aprocess for producing a polyolefin-based resin composition whichcomprises: in a first polymerization stage, polymerizing orcopolymerizing at least one monomer selected from the group consistingof ethylene, propylene, an α-olefin comprising 4 to 20 carbon atoms, astyrene and a cyclic olefin, in the presence of a catalyst comprising acombination of a catalytic component (A) comprising at least onecompound selected from compounds of transitions metals of Group 4 of thePeriodic Table comprising a cyclopentadienyl skeleton structure and apromoter component (B), thereby obtaining a homopolymer or a copolymer;and in a second polymerization stage, copolymerizing the homopolymer orthe copolymer obtained in the first polymerization stage with at leastone monomer selected from the group consisting of ethylene, an α-olefincomprising 4 to 20 carbon atoms, a styrene and a cyclic olefin, in thepresence of a polyene having at least two polymerizable carbon-carbondouble bonds in one molecule, wherein the polyene is at least onecompound selected from the group consisting of a polyene of astyrene-compound, a styrene/α-olefin polyene which comprises a residuegroup of styrene and a residue group of an α-olefin in the samemolecule, a compound of formula (VI)

wherein n is 0, 1, or 2, a compound of formula (VII)

wherein n is 0, 1, or 2, and m is an integer of from 1 to 11, and acompound of formula (VIII)

wherein n is an integer of from 0 to 6; the polyene being used in anamount of 1.0×10⁻⁷ to 1.0×10⁻³ moles per 1 g of the homopolymer or thecopolymer obtained in the first polymerization stage, with the provisothat, in the second polymerization stage, the homopolymer or thecopolymer obtained in the first polymerization stage is not polymerizedwith propylene, and wherein the composition produced by the processsatisfies the following requirements (a) to (c); (a) the intrinsicviscosity [η]2 of a polyolefin obtained in the second polymerizationstage is greater than the intrinsic viscosity [η]1 of a polyolefinobtained in the first polymerization stage, (b) a ratio [η]2/[η]1=1.05to 10, and (c) a content of the polyolefin obtained in the secondpolymerization stage in the polyolefin-based resin composition is 0.00 1to 80% by weight.
 4. The process according to any one of claims 1, 2 or3, wherein said catalyst component (A) is at least one compound selectedfrom the group consisting of a transition metal compound as component(A-1) represented by general formula (I):CpM¹R¹ _(a)R² _(b)R³ _(c)  (I); a transition metal compound as component(A-2) represented by general formula (II):Cp₂M¹R¹ _(a)R² _(e)  (II); a transition metal compound as component(A-3) represented by general formula (III):(Cp-A-Cp)M¹R¹ _(d)R² _(e)  (III); wherein M¹ represents a transitionmetal of Group 4 of the Periodic Table, Cp represents a group selectedfrom the group consisting of a cyclopentadienyl group, a substitutedcyclopentadienyl group, an indenyl group, a substituted indenyl group, atetrahydroindenyl group, a substituted tetrahydroindenyl group, afluorenyl group and a substituted fluorenyl group, wherein R¹, R² and R³each independently represent a ligand, wherein A represents acrosslinking with a covalent bond, wherein a, b and c each represent aninteger of 0 to 3, wherein d and e each represent an integer of 0 to 2,wherein two or more ligands represented by R¹, R² and R³ may be bondedwith each other and form a ring, and wherein two Cp in general formula(II) and (III) may represent a same group or different groups; atransition metal compound as component (A-4) represented by generalformula (IV):

wherein M² represents a titanium atom, a zirconium atom or a hafniumatom, wherein E¹ and E² each represent a ligand selected from the groupconsisting of a cyclopentadienyl group, a substituted cyclopentadienylgroup, an indenyl group, a substituted indenyl group, aheterocyclopentadienyl group, a substituted heterocyclopentadienylgroup, an amide group, a phosphide group, a hydrocarbon group and agroup having a silicon atom, wherein E¹ and E² form crosslinkingstructures via groups represented by A¹ and A², wherein E¹ and E² mayrepresent a same group or different groups, wherein X¹ represents aligand forming a σ-bond, wherein a plurality of X¹ may represent a sameligand or different ligands when the plurality of X¹ are present, theligand represented by X¹ may form a crosslinking structure incombination with another ligand represented by X¹, a ligand representedby E¹ or E² or a Lewis base represented by Y¹, wherein Y¹ represents aLewis base, wherein a plurality of Y¹ may represent a same Lewis base ordifferent Lewis bases when the plurality of Y¹ are present, the Lewisbase represented by Y¹ may form a crosslinking structure in combinationwith another Lewis base represented by Y¹ or a ligand represented by E¹,E² or X¹, wherein A¹ and A² each represent a divalent crosslinking groupwhich bonds two ligands and is a hydrocarbon group comprising 1 to 20carbon atoms, a hydrocarbon group comprising 1 to 20 carbon atoms and atleast one halogen atom, a group comprising a silicon atom, a groupcomprising a germanium atom, a group comprising a tin atom, —O—, —CO—,—S—, —SO₂—, —Se—, —NR⁴—, —PR⁴—, —P(O)R⁴—, —BR⁴— or —AlR⁴—, wherein R⁴ isa hydrogen atom, a halogen atom, a hydrocarbon group comprising 1 to 20carbon atoms or a hydrocarbon group comprising 1 to 20 carbon atoms andat least one halogen atom, and atoms and groups represented by aplurality of R⁴ being a same with or different from each other, qrepresents an integer of 1 to 5 which is [(a valence of the atomrepresented by M²)-2] and r represents an integer of 0 to 3; and atransition metal compound as component (A-5) represented by generalformula (V):

wherein M³ represents a titanium atom, a zirconium atom or a hafniumatom, Cp represents a cyclic unsaturated hydrocarbon group, wherein X²represents hydrogen atom, a halogen atom, an alkyl group comprising 1 to20 carbon atoms, an aryl group comprising 6 to 20 carbon atoms, analkylaryl group comprising 6 to 20 carbon atoms, an arylalkyl groupcomprising 6 to 20 carbon atoms or an alkoxyl group comprising 1 to 20carbon atoms, wherein Z represents SiR⁵ ₂, CR⁵ ₂, SiR⁵ ₂SiR⁵ ₂, CR⁵ ₂CR⁵₂, CR⁵ ₂CR⁵ ₂CR⁵ ₂, CR⁵═CR⁵, CR⁵ ₂SiR⁵ ₂ or GeR⁵ ₂, Y² represents—N(R6)—, —O—, —S— or —P(R⁶)—, wherein R⁵ represents an alkyl group, anaryl group, a silyl group, a halogenated alkyl group or a halogenatedaryl group each comprising hydrogen atom or 20 or less atoms which arenot hydrogen atom or a group comprising a combination of these groups,and wherein R⁶ represents an alkyl group comprising 1 to 10 carbonatoms, an aryl group comprising 6 to 10 carbon atoms or a cyclic systemcomprising at least one R⁵ group and 30 or less atoms which are nothydrogen atom, and s represents a number of 1 or 2; and wherein saidpromoter component (B) is at least one substance selected from the groupconsisting of aluminoxanes as component (B-1), ionic compounds ascomponent (B-2) which can be converted into a cation by a reaction withthe transition metal compound and clay, and as component (B-3) clayminerals and ion exchageable lamellar compounds.
 5. The processaccording to any one of claims 1, 2, or 3, wherein said polyene is apolyene of a styrene/α-olefin polyene which comprises a residue group ofstyrene and a residue group of an α-olefin in a same molecule.
 6. Aprocess for producing a polyolefin-based resin composition, the processcomprising: in a first polymerization stage, polymerizing orcopolymerizing at least one monomer selected from the group consistingof ethylene, propylene and an α-olefin comprising 4 to 20 carbon atoms,in a presence of a catalyst comprising a combination of a catalystcomponent (X-2) comprising (i) a titanium compound, (ii) a magnesiumcompound, (iii) an electron-donating compound (a), an organoaluminumcompound (Y), and an electron-donating compound (b), wherein a halogenelement presents in at least one of (i) the titanium compound, (ii) themagnesium compound, and the organoaluminum compound (Y), and in a secondpolymerization stage, copolymerizing the homopolymer or the copolymerobtained in the first polymerization stage with at least one monomerselected from the group consisting of propylene and an α-olefinconsisting of 4 to 20 carbon atoms, in a presence of a polyenecomprising at least two polymerizable carbon-carbon double bonds in onemolecule; with the proviso that, in the second polymerization stage, thehomopolymer or the copolymer obtained in the first polymerization stageis not polymerized with ethylene, and wherein the produced compositionsatisfying following requirements (a) to (c): (a) a ratio [η]₂/[η]₁=1.05to 10, wherein [η]₁ represents an intrinsic viscosity of a polyolefinobtained in the first polymerization stage and [η]₂ represents anintrinsic viscosity of a polyolefin obtained in the secondpolymerization stage, (b) a content of the polyolefin obtained in thesecond polymerization stage in the polyolefin-based resin composition is0.01 to 80% by weight, and (c) no insoluble components are present in adissolution test of the polyolefin-based resin composition using decalinat 135° C. as a solvent.
 7. The process according to claim 6, whereinthe at least one monomer polymerized in said second polymerization stagecomprises propylene.